Rechargeable battery with internal current limiter and interrupter

ABSTRACT

A high energy density rechargeable (HEDR) battery employs a combined current limiter/current interrupter to prevent thermal runaway in the event of internal discharge or other disruption of the separator. The combined current limiter/current interrupter is interior to the battery.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a national stage entry, filed under 35 U.S.C. § 371,of International Application No. PCT/US2015/062767, filed on Nov. 25,2015, and claims priority to the following five ProvisionalApplications: U.S. Provisional Application No. 62/084,454, filed Nov.25, 2014, titled “Battery Safety Device;” U.S. Provisional ApplicationNo. 62/114,001, filed Feb. 9, 2015, titled “Rechargeable Battery withResistive Layer for Enhanced Safety;” U.S. Provisional Application No.62/114,006, filed Feb. 9, 2015, titled “Rechargeable Battery withTemperature Activated Current Interrupter;” U.S. Provisional ApplicationNo. 62/114,007, filed Feb. 9, 2015, titled “Rechargeable Battery withVoltage Current Interrupter;” and U.S. Provisional Application No.62/114,508, filed Feb. 10, 2015, titled “Rechargeable Battery withInternal Current Limiter and Interrupter;” as well as to U.S. patentapplication Ser. No. 14/714,160, now U.S. Pat. No. 10,396,341, filed May15, 2015, titled “Rechargeable Battery With Internal Current Limiter AndInterrupter,” which claims priority to U.S. Provisional Application No.62/084,454, filed Nov. 25, 2014, titled “Battery Safety Device,” andU.S. Provisional Application No. 62/114,508, filed Feb. 10, 2015, titled“Rechargeable Battery with Internal Current Limiter and Interrupter.”The disclosures of which are all hereby incorporated by referenceherein, each in its entirety.

BACKGROUND Technical Field

This disclosure relates to an internal current limiter or currentinterrupter used to protect a battery in the event of an internal shortcircuit or overcharge leads to thermal runaway. In particular, itrelates to a high energy density rechargeable (HEDR) battery withimproved safety.

Background

There is a need for rechargeable battery systems with enhanced safetywhich have a high energy density and hence are capable of storing anddelivering large amounts of electrical energy per unit volume and/orweight. Such stable high energy battery systems have significant utilityin a number of applications including military equipment, communicationequipment, and robotics.

An example of a high energy density rechargeable (HEDR) battery commonlyin use is the lithium-ion battery.

A lithium-ion battery is a rechargeable battery wherein lithium ionsmove from the negative electrode to the positive electrode duringdischarge and back when charging. Lithium-ion batteries can be dangerousunder some conditions and can pose a safety hazard. The fire energycontent (electrical+chemical) of lithium cobalt-oxide cells is about 100to 150 kJ per A-h, most of it chemical. If overcharged or overheated,Li-ion batteries may suffer thermal runaway and cell rupture. In extremecases this can lead to combustion. Also, short-circuiting the battery,either externally or internally, will cause the battery to overheat andpossibly to catch fire.

Overcharge:

In a lithium-ion battery, useful work is performed when electrons flowthrough a closed external circuit. However, in order to maintain chargeneutrality, for each electron that flows through the external circuit,there must be a corresponding lithium ion that is transported from oneelectrode to the other. The electric potential driving this transport isachieved by oxidizing a transition metal. For example, cobalt (Co), fromCo³⁺ to Co⁴⁺ during charge and reduced from Co⁴⁺ to Co³⁺ duringdischarge. Conventionally, Li_(1-χ)CoO₂ may be employed, where thecoefficient χ represents the molar fraction of both the Li ion and theoxidative state of CoO₂, viz., Co³° or Co⁴⁺. Employing theseconventions, the positive electrode half-reaction for the lithium cobaltbattery is represented as follows:LiCoO₂

Li_(1-χ)CoO₂+χLi⁺ +χe ⁻The negative electrode half reaction is represented as follows:χLi⁺ +χe ⁻ +xC₆

χLiC₆The cobalt electrode reaction is reversible limited to x<0.5, limitingthe depth of discharge allowable because of cycle life considerationsand the stability of LiCoO₂. Overcharge leads to the synthesis of cobalt(IV) oxide, as follows:LiCoO₂→Li⁺+CoO₂+O₂ +e ⁻LiCoO₂ will decompose into CoO₂ and release a large amount of heat andoxygen. The released oxygen will then oxidize the electrolyte, whichwill lead to thermal runaway. This process is irreversible. Therefore,what is needed is some device or design that can decompose below orbefore positive decomposition. This device will protect the cell fromthermal runaway.Thermal Runaway:

If the heat generated by a lithium ion battery exceeds its heatdissipation capacity, the battery can become susceptible to thermalrunaway, resulting in overheating and, under some circumstances, todestructive results such as fire or violent explosion. Thermal runawayis a positive feedback loop wherein an increase in temperature changesthe system so as to cause further increases in temperature. The excessheat can result from battery mismanagement, battery defect, accident, orother causes. However, the excess heat generation often results fromincreased joule heating due to excessive internal current or fromexothermic reactions between the positive and negative electrodes.Excessive internal current can result from a variety of causes, but alowering of the internal resistance due to separator short circuitcaused by the factors such as conductive particles spearing through theseparator is one possible cause. Heat resulting from a separator shortcircuit can cause a further breach within the separator, leading to amixing of the reagents of the negative and positive electrodes and thegeneration of further heat due to the resultant exothermic reaction.

Internal Short Circuit:

Lithium ion batteries employ a separator between the negative andpositive electrodes to electrically separate the two electrodes from oneanother while allowing lithium ions to pass through. When the batteryperforms work by passing electrons through an external circuit, thepermeability of the separator to lithium ions enables the battery toclose the circuit. Short circuiting the separator by providing aconductive path across it allows the battery to discharge rapidly. Ashort circuit across the separator can result from improper charging anddischarging or cell manufacturing defects such as metal impurities andmetal shard formation during electrode production. More particularly,improper charging can lead to the deposition of metallic lithiumdendrites on the surface of the negative electrode and these dendritesgrow to penetrate the separator through the nanopores so as to provide aconductive path for electrons from one electrode to the other. Inaddition, improper discharge at or below 1.5V will cause copperdissolution which can ultimately lead to the formation of metalliccopper dendrites on the surface of the negative electrode which can alsogrow to penetrate the separator through the nanopore. The lowerresistance of these conductive paths allows for rapid discharge and thegeneration of significant joule heat. Overheating and thermal runawaycan result.

What was needed was a combination internal current limiter and currentinterrupter that could, at first, limit the rate of internal dischargeresulting from an internal short circuit so as to reduce the generationof Joule heat, if the rate of internal discharge is insufficientlylimited, could also interrupt the internal short circuit to furthercurtail the rate of internal discharge, regardless of the temperatureincrease, so as to avert fire and/or explosion.

SUMMARY

In a first aspect, provided in some implementations herein is animproved high energy density rechargeable (HEDR) battery of a typeincluding two electrodes of opposite polarity, each electrodecharacterized by its resistivity, by its safe operating temperaturerange, and its safe charging voltage; and a separator for separating thetwo electrodes and preventing internal discharge therebetween. The HEDRbattery includes at least one electrode employing a current collectorfor transferring electrons, with the separator being subject to a riskof forming a short circuit, the short circuit potentially allowing arapid internal discharge between the two electrodes, the rapid internaldischarge between the two electrodes potentially allowing a rapidproduction of joule heat therefrom, the rapid production of joule heatpotentially allowing a thermal runaway. In the HEDR battery, the twoelectrodes can be subject to a risk of overcharge above the safecharging voltage and the formation of the short circuit therefrom andthe two electrodes can be subject to a risk of thermal runaway above thesafe operating temperature range. The HEDR battery can include animprovement for slowing the rate of internal discharge resulting fromthe short circuit, for slowing the production of joule heat therefrom,and for reducing the risk of thermal runaway, the improvement includes:a current limiter forming an electrical coupling between one of theelectrodes and its corresponding current collector, the current limiterhaving a resistivity for resistively impeding current therethrough and,in the event the separator forms the short circuit, for divertingcurrent from the electrode current collector to which it is coupled, andfor reducing the rate of the internal discharge between the twoelectrodes; and a current interrupter having an engaged configuration,an disengaged configuration, and a gas generating component fortransitioning the current interrupter from the engaged to the unengagedconfiguration. The gas generating component can have a trigger forgenerating a gas, the trigger being selected from the group consistingof temperature triggers and voltage triggers, and the temperaturetriggers can be activatable above the safe operating temperature range.The voltage triggers can be activatable above the safe charging voltagein the engaged configuration, the current interrupter electricallycoupling one of the electrodes and its corresponding current collectorwith a laminated connection, and in the disengaged configuration, thelaminated connection becoming delaminated and the current interrupterforming a nonconductive gap for interrupting the electrical couplingbetween the electrode and its corresponding current collector. Thecurrent interrupter transitions from the engaged to the disengagedconfiguration by triggering the gas generating component responsive tothe trigger, the generated gas delaminating the laminated connection forinterrupting the electrical coupling between the electrode and itscorresponding current collector. The current limiter and the currentinterrupter, in combination, diminish the risk of thermal runawayresulting from separator short circuit, electrode overcharge, andelectrode overheating.

The following features can be present in the improved high energydensity rechargeable (HEDR) battery in any suitable combination. Thecurrent limiter and the current interrupter can be simultaneouslyincorporated into a protective layer interposed by lamination betweenthe same electrode and current collector. The HEDR battery can includetwo current collectors, including a first current collector and a secondcurrent collector, the two electrodes including a first electrode and asecond electrode, and the first electrode including a first portion anda second portion, the second portion of the first electrode interposedbetween the first portion of the first electrode and the first currentcollector, the improvement further characterized in which: the currentlimiter being layered between the first portion of the first electrodeand the second portion of the first electrode; and the currentinterrupter being layered between the second portion of the firstelectrode and the first current collector. The current limiter can belayered between the second portion of the first electrode and the firstcurrent collector, and the current interrupter can be layered betweenthe first portion of the first electrode and the second portion of thefirst electrode. The HEDR battery can have two current collectors,including a first current collector and a second current collector andthe two electrodes including a first electrode and a second electrode,and the current limiter can be layered between the first electrode andthe first current collector; and the current interrupter can be layeredbetween the second electrode and the second current collector. In theHEDR battery, each electrode can have a temperature range for safeoperation and an internal resistivity therein, and the current limitercan have a resistivity greater than the internal resistivity of theelectrode with which the current limiter is layered within thetemperature range for safe operation. The current limiter can lack aresistivity transition switch at temperatures within the temperaturerange for safe operation. The HEDR battery can be such that eachelectrode has a temperature range for standard operation and the currentlimiter can have a resistivity transition with a resistivity less thanthe internal resistivity of the electrode within the temperature rangefor standard operation and a resistivity greater than the internalresistivity of the electrode above the temperature range for standardoperation. The HEDR battery can be such that each electrode has atemperature range for standard operation and the current interrupter canbe activated by temperature above the temperature range for standardoperation. In some implementations, the HEDR battery can be of a type inwhich each electrode has a temperature range for standard operation anda temperature range for safe operation, an in which the currentinterrupter can be activated by temperature above the temperature rangefor standard operation and within the temperature range for safeoperation. In some implementations, the HEDR battery can be such thateach electrode has an internal resistivity within the temperature rangefor safe operation, in which the current limiter can have a resistivitygreater than the internal resistivity of the electrode with which thecurrent limiter is layered within the temperature range for safeoperation. The current limiter and the current interrupter can besimultaneously incorporated into a protective layer interposed bylamination between the same electrode and current collector. The HEDRbattery can be of a type in which each electrode has a voltage range forstandard operation, and in which the current interrupter is activated byvoltage above the voltage range for standard operation. The HEDR batterycan be of a type in which each electrode has a voltage range forstandard operation and a voltage range for safe operation, and in whichthe current interrupter is activated by voltage above the voltage rangefor standard operation and within the voltage range for safe operation.The current limiter and the current interrupter can be simultaneouslyincorporated into a protective layer interposed by lamination betweenthe same electrode and current collector.

In a related aspect, provided herein is an improved high energy densityrechargeable battery of a type including two electrodes of oppositepolarity, a separator separating the two electrodes, and at least onecurrent collector electrically coupled to one of the electrodes, theseparator preventing internal discharge between the two electrodes,failure of the separator potentially causing an internal dischargebetween the two electrodes, the internal discharge causing a generationof joule heat of potential danger, that includes a thermally activatablecurrent interrupter and a voltage activatable current interrupter. Thethermally activatable current interrupter can be layered by laminationbetween one of the current collectors and one of the electrodes, thethermally activatable current interrupter, when unactivated,electrically coupling the current collector to the electrode with whichit is layered, the current interrupter, when activated, delaminatingfrom the current collector for forming a nonconductive gap forelectrically decoupling the current collector from the electrode withwhich it had been layered, the electrical decoupling slowing the rate ofinternal discharge between the two electrodes in the event of separatorfailure. The voltage activatable current interrupter can be layered bylamination between one of the current collectors and one of theelectrodes, the voltage activatable current interrupter, whenunactivated, electrically coupling the current collector to theelectrode with which it is layered, the current interrupter, whenactivated, delaminating from the current collector for forming anonconductive gap for electrically decoupling the current collector fromthe electrode with which it had been layered, the electrical decouplingslowing the rate of internal discharge between the two electrodes in theevent of separator failure. In the HEDR battery, the activation ofeither the thermally activated current interrupter or voltage activatedcurrent interrupter in the event of separator failure, can slow thegeneration joule heat for diminishing the potential danger.

In a further related aspect, provided in some implementations herein isa process for avoiding thermal runaway within a high energy densityrechargeable battery undergoing internal discharge due to separatorfailure, that includes delaminating an electrode within the battery fromits current collector by generating a gas from a heat sensitive gasgenerating material within an interrupt layer interposed between theelectrode and current collector, the delaminating electricallydecoupling the electrode from its current collector for slowing the rateof internal discharge.

In a first aspect, provided herein is a high energy density rechargeable(HEDR) battery that includes an anode energy layer, a cathode energylayer, a separator between the anode energy layer and the cathode energylayer for preventing internal discharge thereof, at least one currentcollector for transferring electrons to and from either the anode orcathode energy layer, the anode and cathode energy layers each having aninternal resistivity, the HEDR battery having a preferred temperaturerange for discharging electric current and an upper temperature safetylimit; and a resistive layer interposed between the separator and one ofthe current collectors, the resistive layer configured to limit the rateof internal discharge through the separator in the event of separatorfailure and the generation of joule heat resulting therefrom, theresistive layer having a fixed resistivity at temperatures between thepreferred temperature range and the upper temperature safety limit, thefixed resistivity of the resistive layer being greater than the internalresistivity of either energy layer, the resistive layer for avoidingtemperatures in excess of the upper temperature safety limit in theevent of separator failure.

The following features can be included in the HEDR battery in anysuitable combination. In some implementations, the resistive layer ofthe HEDR battery can be porous and include a ceramic powder defining aninterstitial space, a binder for partially filling the interstitialspace for binding the ceramic powder; and a conductive componentdispersed within the binder for imparting resistivity to the resistivelayer, the interstitial space remaining partially unfilled for impartingporosity and permeability to the resistive layer. The resistive layercan be compressed to reduce the unfilled interstitial space and increasethe binding of the ceramic powder by the binder. The resistive layer caninclude greater than 30% ceramic powder by weight. The resistive layercan include greater than 50% ceramic powder by weight. The resistivelayer can include greater than 70% ceramic powder by weight. Theresistive layer can include greater than 75% ceramic powder by weight.The resistive layer can include greater than 80% ceramic powder byweight. The resistive layer of the HEDR battery can be permeable totransport of ionic charge carriers. The resistive layer can benon-porous and have a composition that includes a non-conductive filler,a binder for binding the non-conductive filler, and a conductivecomponent dispersed within the binder for imparting resistivity to theresistive layer. The resistive layer can be impermeable to transport ofionic charge carriers. The fixed resistivity of the resistive layer ofthe HEDR battery can be at least twice as great as the internalresistivity of either energy layer. The fixed resistivity of theresistive layer can be at least five times as great as the internalresistivity of either energy layer. The fixed resistivity of theresistive layer can be at least ten times as great as the internalresistivity of either energy layer. The resistive layer can lack atransformation from solid phase to non-solid phase for transforming theresistivity of the resistive layer from low resistivity to highresistivity at temperatures between the maximum operating temperatureand the upper temperature safety limit. The resistive layer can benon-sacrificial at temperatures below the upper temperature safetylimit. The resistive layer can be sacrificial at temperatures above theupper temperature safety limit. The resistive layer can include aceramic powder that chemically decomposes above the upper temperaturesafety limit for evolving a fire retardant gas. The resistive layer caninclude a ceramic powder that chemically decomposes above the uppertemperature safety limit for evolving a gas for delaminating the currentcollector from the resistive layer. The current collector can include ananode current collector for transferring electrons to and from the anodeenergy layer, wherein the resistive layer is interposed between theseparator and the anode current collector. The resistive layer can beinterposed between the anode current collector and the anode energylayer. The resistive layer can be interposed between the anode energylayer and the separator. In some implementations, the anode energy layerof the HEDR battery can include a first anode energy layer, and a secondanode energy layer interposed between the first anode energy and theseparator, wherein the resistive layer is interposed between the firstanode energy layer and the second anode energy layer. The currentcollector can include a cathode current collector for transferringelectrons to and from the cathode energy layer, wherein the resistivelayer is interposed between the separator and the cathode currentcollector. The resistive layer can be interposed between the cathodecurrent collector and the cathode energy layer. The resistive layer canbe interposed between the cathode energy layer and the separator. Thecathode energy layer can include a first cathode energy layer, and asecond cathode energy layer interposed between the first cathode energyand the separator, wherein the resistive layer is interposed between thefirst cathode energy layer and the second cathode energy layer. In someimplementations, the HEDR battery can include two current collectorsthat include an anode current collector for transferring electrons toand from the anode energy layer, and a cathode current collector fortransferring electrons to and from the cathode energy layer in which theresistive layer comprises an anode resistive layer and a cathoderesistive layer, the anode resistive layer interposed between theseparator and the anode current collector, the cathode resistive layerinterposed between the separator and the cathode current collector.

In a related aspect, provided herein is a method for limiting the rateof an internal discharge of energy layers resulting from a separatorfailure within a high energy density rechargeable (HEDR) battery, themethod that includes resisting the internal discharge with a resistivelayer, the resistive layer being interposed between a separator and acurrent collector within the HEDR battery, the resistive layer having afixed resistivity at temperatures between a preferred temperature rangefor discharging the energy layers and an upper temperature safety limit,the fixed resistivity of the resistive layer being greater than theinternal resistivity of the energy layers.

Provided in some embodiments herein is a high energy densityrechargeable (HEDR) metal-ion battery that includes an anode energylayer, a cathode energy layer, a separator for separating the anodeenergy layer from the cathode energy layer, at least one currentcollector for transferring electrons to and from either the anode orcathode energy layer, the high energy density rechargeable metal-ionbattery having an upper temperature safety limit for avoiding thermalrunaway, and an interrupt layer activatable for interrupting currentwithin high energy density rechargeable metal-ion battery upon exposureto temperature at or above the upper temperature safety limit, theinterrupt layer interposed between the separator and one of the currentcollectors, the interrupt layer, when unactivated, being laminatedbetween the separator and one of the current collectors for conductingcurrent therethrough, the interrupt layer, when activated, beingdelaminated for interrupting current through the high energy densityrechargeable metal-ion battery, the interrupt layer including atemperature sensitive decomposable component for decomposing uponexposure to temperature at or above the upper temperature safety limit,the temperature sensitive decomposable component for evolving a gas upondecomposition, the evolved gas for delaminating the interrupt layer forinterrupting current through the high energy density metal-ion battery,in which the high energy density rechargeable metal-ion battery avoidsthermal runaway by activation of the interrupt layer upon exposure totemperature at or above the upper temperature safety limit forinterrupting current in high energy density rechargeable metal-ionbattery.

The following features can be present in the HEDR metal-ion battery inany suitable combination. The interrupt layer can be porous. Thetemperature sensitive decomposable component can include a ceramicpowder. The interrupt layer can have a composition comprising theceramic powder, a binder, and a conductive component. The ceramic powdercan define an interstitial space. The binder can partially fill theinterstitial space for binding the ceramic powder. The conductivecomponent can be dispersed within the binder for imparting conductivityto the interrupt layer. The interstitial space can remain partiallyunfilled for imparting porosity and permeability to the interrupt layer.The interrupt layer can include greater than 30% ceramic powder byweight. The interrupt layer can include greater than 50% ceramic powderby weight. The interrupt layer can include greater than 70% ceramicpowder by weight. The interrupt layer can include greater than 75%ceramic powder by weight. The interrupt layer can include greater than80% ceramic powder by weight. The interrupt layer can be permeable totransport of ionic charge carriers. The interrupt layer can benon-porous and have a composition that includes a non-conductive filler,a binder for binding the non-conductive filler, and a conductivecomponent dispersed within the binder for imparting conductivity to theinterrupt layer. The interrupt layer can be impermeable to transport ofionic charge carriers. The interrupt layer can be sacrificial attemperatures above the upper temperature safety limit. The interruptlayer can include a ceramic powder that chemically decomposes above theupper temperature safety limit for evolving a fire retardant gas. Thecurrent collector can include an anode current collector fortransferring electrons to and from the anode energy layer, wherein theinterrupt layer being interposed between the separator and the anodecurrent collector. The interrupt layer can be interposed between theanode current collector and the anode energy layer. The interrupt layercan be interposed between the anode energy layer and the separator. Theanode energy layer of the HEDR battery can include a first anode energylayer; and a second anode energy layer interposed between the firstanode energy and the separator, wherein the interrupt layer beinginterposed between the first anode energy layer and the second anodeenergy layer. The current collector can include a cathode currentcollector for transferring electrons to and from the cathode energylayer, wherein the interrupt layer is interposed between the separatorand the cathode current collector. The interrupt layer can be interposedbetween the cathode current collector and the cathode energy layer. Theinterrupt layer can be interposed between the cathode energy layer andthe separator. The cathode energy layer can include a first cathodeenergy layer and a second cathode energy layer interposed between thefirst cathode energy and the separator, wherein the interrupt layer isinterposed between the first cathode energy layer and the second cathodeenergy layer. The HEDR battery can further include two currentcollectors that include an anode current collector for transferringelectrons to and from the anode energy layer and a cathode currentcollector for transferring electrons to and from the cathode energylayer, in which the interrupt layer includes an anode interrupt layerand a cathode interrupt layer, the anode interrupt layer interposedbetween the separator and the anode current collector, the cathodeinterrupt layer interposed between the separator and the cathode currentcollector.

In a related aspect, a method is presented for interrupting currentwithin a high energy density rechargeable metal-ion battery uponexposure to temperature at or above an upper temperature safety limitfor avoiding thermal runaway, that includes: raising the temperature ofthe high energy density rechargeable metal-ion battery above the uppertemperature safety limit, and activating the interrupt layer forinterrupting current through the high energy density metal-ion battery.The high energy density rechargeable metal-ion battery can include: ananode energy layer; a cathode energy layer; a separator separating theanode energy layer from the cathode energy layer; a current collectorfor transferring electrons to and from either the anode or cathodeenergy layer; and an interrupt layer, the interrupt layer interposedbetween the separator and one of the current collectors, the interruptlayer, when unactivated, being laminated between the separator and oneof the current collectors for conducting current therethrough, theinterrupt layer, when activated, being delaminated for interruptingcurrent through the lithium ion battery, the interrupt layer comprisinga temperature sensitive decomposable component for decomposing uponexposure to temperature at or above the upper temperature safety limit,the temperature sensitive decomposable component for evolving a gas upondecomposition, the evolved gas for delaminating the interrupt layer forinterrupting current through the high energy density metal-ion battery;whereby thermal runaway by the high energy density rechargeablemetal-ion battery is avoided by interruption of current therethrough.

Provided in some implementations herein is a high energy densityrechargeable (HEDR) metal-ion battery that includes an anode energylayer, a cathode energy layer, a separator for separating the anodeenergy layer from the cathode energy layer, an anode current collectorfor transferring electrons to and from the anode energy layer, the highenergy density rechargeable metal-ion battery being rechargeable andcharacterized by a maximum safe voltage for avoiding overcharge; and aninterrupt layer activatable for interrupting current within the highenergy density rechargeable battery upon exposure to voltage in excessof the maximum safe voltage, the interrupt layer sandwiched between thecathode energy layer and the cathode current collector, the interruptlayer, when unactivated, being laminated to the anode current collectorfor conducting current therethrough, the interrupt layer, whenactivated, being delaminated from the anode current collector forinterrupting current therethrough, the interrupt layer including avoltage sensitive decomposable component for decomposing upon exposureto voltage in excess of the maximum safe voltage, the voltage sensitivedecomposable component for evolving a gas upon decomposition, theevolved gas for delaminating the interrupt layer from the anode currentcollector for interrupting current therethrough, whereby the high energydensity rechargeable metal-ion battery avoids overcharge by activationof the interrupt layer upon exposure to voltage in excess of the maximumsafe voltage for interrupting current therethough.

The following features can be present in the high energy densityrechargeable metal-ion battery in any suitable combination. Theinterrupt layer of the HEDR battery can be porous and have a compositionthat includes a ceramic powder defining an interstitial space; a binderfor partially filling the interstitial space for binding the ceramicpowder; and a conductive component dispersed within the binder forimparting conductivity to the interrupt layer, the interstitial spaceremaining partially unfilled for imparting porosity and permeability tothe interrupt layer. The interrupt layer can be compacted for reducingthe unfilled interstitial space and increasing the binding of theceramic powder by the binder. The interrupt layer can include greaterthan 30% ceramic powder by weight. The interrupt layer can includegreater than 50% ceramic powder by weight. The interrupt layer caninclude greater than 70% ceramic powder by weight. The interrupt layercan include greater than 75% ceramic powder by weight. The interruptlayer can include greater than 80% ceramic powder by weight. Theinterrupt layer can be permeable for transporting ionic charge carriers.The interrupt layer of the HEDR battery can be non-porous and have acomposition that includes a non-conductive filler; a binder for bindingthe non-conductive filler; and a conductive component dispersed withinthe binder for imparting conductivity to the interrupt layer. Theinterrupt layer can be impermeable to transport of ionic chargecarriers. The interrupt layer can be sacrificial at voltages above themaximum safe voltage for recharging. The interrupt layer can include aceramic powder that chemically decomposes above maximum safe voltage forevolving the gas. The gas can be fire retardant.

In a related aspect, provided herein is a method for interrupting arecharging process for a high energy density rechargeable metal-ionbattery upon exposure to voltage at or above a maximum safe voltage foravoiding overcharge, the high energy density rechargeable metal-ionbattery comprising an anode energy layer, a cathode energy layer, aseparator between the anode energy layer and the cathode energy layer,and an anode current collector for transferring electrons to and fromthe anode energy layer. The method includes overcharging the high energydensity rechargeable metal-ion battery for increasing the voltage abovethe maximum safe voltage for recharging; and interrupting theovercharging by evolving a gas by decomposition of a voltage sensitivedecomposable component within a interrupt layer laminated to the anodecurrent collector, the evolved gas delaminating the interrupt layer fromthe anode current collector, whereby the overcharging of the high energydensity rechargeable metal-ion battery is interrupted by evolution ofgas within the interrupt layer for delaminating the interrupt layer fromthe anode current collector.

A first aspect of the disclosure is directed to an improved high energydensity rechargeable (HEDR) battery of a type including two electrodesof opposite polarity (12 and 14). Each electrode is characterized by itsresistivity, by its safe operating temperature range, and its safecharging voltage. The HEDR is further of a type having a separator 2 forseparating the two electrodes (12 and 14) and preventing internaldischarge there between and at least one electrode (12 or 14) employinga current collector 4 for transferring electrons. The separator 2 issubject to a risk of forming a short circuit. The short circuit canpotentially allow a rapid internal discharge between the two electrodes(12 and 14), potentially allowing a rapid production of joule heattherefrom, the rapid production of joule heat potentially allowing athermal runaway. The two electrodes (12 and 14) are subject to a risk ofovercharge above the safe charging voltage and the formation of theshort circuit therefrom. The two electrodes (12 and 14) are subject to arisk of thermal runaway above the safe operating temperature range.

The improvement for this first aspect of the disclosure is employablefor slowing the rate of internal discharge resulting from the shortcircuit, for slowing the production of joule heat therefrom, and forreducing the risk of thermal runaway.

The improvement comprises the addition to the HEDR battery of a currentlimiter 6 combined with a current interrupter 8.

The current limiter 6 forms an electrical coupling between one of theelectrodes (12 or 14) and its corresponding current collector 4. Thecurrent limiter 6 has a resistivity for resistively impeding currenttherethrough and, in the event the separator 2 forms the short circuit,for diverting current from the electrode current collector 4 to which itis coupled, and for reducing the rate of the internal discharge betweenthe two electrodes (12 and 14).

The current interrupter 8 has an engaged configuration, a disengagedconfiguration, and a gas generating component for transitioning thecurrent interrupter 8 from the engaged to the unengaged configuration.The gas generating component also has a trigger for generating a gas.The trigger is selected from the group consisting of temperaturetriggers and voltage triggers.

The temperature triggers are activatable above the safe operatingtemperature range.

The voltage triggers are activatable above the safe charging voltage.

In its engaged configuration, the current interrupter 8 electricallycouples one of the electrodes (12 or 14) and its corresponding currentcollector 4 with a laminated connection.

In the disengaged configuration, the laminated connection becomesdelaminated and the current interrupter 8 forms a nonconductive gap forinterrupting the electrical coupling between the electrode (12 or 14)and its corresponding current collector 4.

The current interrupter 8 transitions from its engaged configuration toits disengaged configuration by triggering the gas generating componentresponsive to the trigger. The resulting generated gas delaminates thelaminated connection for interrupting the electrical coupling betweenthe electrode (12 or 14) and its corresponding current collector 4.

In this first aspect of the disclosure, the current limiter 6 and thecurrent interrupter 8, in combination, diminishes the risk of thermalrunaway resulting from separator short circuit, electrode overcharge,and electrode overheating.

In one embodiment of this first aspect of the disclosure, the currentlimiter 6 and the current interrupter 8 are simultaneously incorporatedinto a protective layer interposed by lamination between the sameelectrode (12 or 14) and current collector 4.

In another embodiment of this first aspect of the disclosure, thebattery is of a type having two current collectors 4, including a firstcurrent collector 4 and a second current collector 4. The two electrodes(12 and 14) include a first electrode and a second electrode. The firstelectrode includes a first portion and a second portion. The secondportion of the first electrode is interposed between the first portionof the first electrode and the first current collector 4. Theimprovement of this embodiment of the disclosure is furthercharacterized by the current limiter 6 being layered between the firstportion of the first electrode and the second portion of the firstelectrode; and the current interrupter 8 being layered between thesecond portion of the first electrode and the first current collector 4.In a sub-embodiment of this first aspect of the disclosure, the currentlimiter 6 is layered between the second portion of the first electrodeand the first current collector 4, and the current interrupter 8 islayered between the first portion of the first electrode and the secondportion of the first electrode.

In another embodiment of this first aspect of the disclosure, thebattery is of a type having two current collectors 4, including a firstcurrent collector 4 and a second current collector 4 and the twoelectrodes (12 and 14) including a first electrode and a secondelectrode, the improvement further characterized wherein. In thisembodiment, the current limiter 6 is layered between the first electrodeand the first current collector 4; and the current interrupter 8 beinglayered between the second electrode and the second current collector 4.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 or 14) has a temperaturerange for safe operation and an internal resistivity therein. In thisembodiment, the current limiter 6 has a resistivity greater than theinternal resistivity of the electrode (12 or 14) with which the currentlimiter 6 is layered within the temperature range for safe operation.

In another embodiment of this first aspect of the disclosure, theimprovement is further characterized by the current limiter 6 lacking aresistivity transition switch at temperatures within the temperaturerange for safe operation.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 and 14) has atemperature range for standard operation. In this embodiment, thecurrent limiter 6 has a resistivity transition with a resistivity lessthan the internal resistivity of the electrode (12 and/or 14) within thetemperature range for standard operation and a resistivity greater thanthe internal resistivity of the electrode (12 and/or 14) above thetemperature range for standard operation.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 and 14) has atemperature range for standard operation. In this embodiment, thecurrent interrupter 8 is activated by temperature above the temperaturerange for standard operation.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 and 14) has atemperature range for standard operation and a temperature range forsafe operation. In this embodiment, the current interrupter 8 isactivated by temperature above the temperature range for standardoperation and within the temperature range for safe operation.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 and 14) has an internalresistivity within the temperature range for safe operation. In thisembodiment, the current limiter 6 has a resistivity greater than theinternal resistivity of the electrode (12 or 14) with which the currentlimiter 6 is layered within the temperature range for safe operation. Inan alternative to this embodiment, the current limiter 6 and the currentinterrupter 8 are simultaneously incorporated into a protective layerinterposed by lamination between the same electrode (12 or 14) andcurrent collector 4.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 and 14) has a voltagerange for standard operation. In this embodiment, the currentinterrupter 8 is activated by voltage above the voltage range forstandard operation.

In another embodiment of this first aspect of the disclosure, thebattery is of a type wherein each electrode (12 and 14) has a voltagerange for standard operation and a voltage range for safe operation. Inthis embodiment, the current interrupter 8 is activated by voltage abovethe temperature range for standard operation and within the voltagerange for safe operation. In an alternative of this embodiment, thecurrent limiter 6 and current interrupter 8 are simultaneouslyincorporated into a protective layer interposed by lamination betweenthe same electrode (12 or 14) and current collector 4.

A second aspect of the disclosure is directed to another improved highenergy density rechargeable battery of a type including two electrodes(12 and 14) of opposite polarity, a separator 2 separating the twoelectrodes (12 and 14), and at least one current collector 4electrically coupled to one of the electrodes (12 or 14). The separator2 prevents internal discharge between the two electrodes (12 and 14).Failure of the separator 2 potentially causes an internal dischargebetween the two electrodes (12 and 14). The internal discharge causesthe generation of joule heat of potential danger.

The improvement for this second aspect of the disclosure comprises athermally activatable current interrupter 8 and a voltage activatablecurrent interrupter 8.

The thermally activatable current interrupter 8 is layered by laminationbetween one of the current collectors 4 and one of the electrodes (12 or14). The thermally activatable current interrupter 8, when unactivated,electrically couples the current collector 4 to the electrode (12 or 14)with which it is layered, the current interrupter 8. When activated, thethermally activatable current interrupter 8 delaminates from the currentcollector 4 for forming a nonconductive gap for electrically decouplingthe current collector 4 from the electrode (12 or 14) with which it hadbeen layered. The electrical decoupling serves to slow the rate ofinternal discharge between the two electrodes (12 and 14) in the eventof separator failure.

The voltage activatable current interrupter 8 is layered by laminationbetween one of the current collectors 4 and one of the electrodes (12 or14). The voltage activatable current interrupter 8, when unactivated,electrically couples the current collector 4 to the electrode (12 or 14)with which it is layered. The current interrupter 8, when activated,delaminates from the current collector 4 by forming a nonconductive gapfor electrically decoupling the current collector 4 from the electrode(12 or 14) with which it had been layered. The resultant electricaldecoupling serves to slow the rate of internal discharge between the twoelectrodes (12 and 14) in the event of separator failure. In this secondaspect of the disclosure, activation of either the thermally activatedcurrent interrupter 8 or the voltage activated current interrupter 8 inthe event of separator failure, slows the generation joule heat fordiminishing the potential danger.

A second aspect of the disclosure is directed to a process for avoidingthermal runaway within a high energy density rechargeable batteryundergoing internal discharge due to separator failure. The processcomprises the step of delaminating an electrode (12 or 14) within thebattery from its current collector 4 by generating a gas from a heatsensitive gas generating material within an interrupt layer interposedbetween the electrode (12 or 14) and current collector 4. Thedelamination electrically decouples the electrode (12 or 14) from itscurrent collector 4 for slowing the rate of internal discharge.

A third aspect of the disclosure is directed to a process for avoidingthermal runaway within a high energy density rechargeable battery atrisk of suffering from separator failure due to voltage overcharge. Theprocess comprises the step of delaminating an electrode (12 or 14)within the battery from its current collector 4 by generating a gas froma voltage sensitive gas generating material within an interrupt layerinterposed between the electrode (12 or 14) and current collector 4. Thedelamination electrically decouples the electrode (12 or 14) from itscurrent collector 4 for interrupting the voltage overcharge.

A fourth aspect of the disclosure is directed to a process for avoidingthermal runaway within a high energy density rechargeable battery atrisk of suffering from separator failure due to voltage overcharge. Theprocess comprises the step of delaminating an electrode (12 or 14)within the battery from its current collector 4 by generating a gas froma voltage or temperature sensitive material that will form the gasindirectly through its decomposition compound (at the high voltage) thatwill react with the battery components such as electrolyte andelectrodes (12 and 14). This voltage or temperature sensitive materialwill be still called as gas generator, and can be within an interruptlayer interposed between the electrode (12 or 14) and current collector4. The delamination electrically decouples the electrode (12 or 14) fromits current collector 4 for interrupting the voltage overcharge.

BRIEF DESCRIPTION OF DRAWINGS

The present disclosure is described more fully herein with reference tothe accompanying drawings, in which some exemplary embodiments of thepresent disclosure are shown. As those skilled in the art would realize,the described embodiments may be modified in various different ways, allwithout departing from the spirit or scope of the present disclosure.Accordingly, the drawings and description are to be regarded asillustrative in nature and not restrictive. In the drawings, thethicknesses of layers and regions may be exaggerated for clarity.

FIGS. 1A-1G illustrate schematic representations of exemplaryconfigurations of film-type lithium ion batteries having one or moreresistive layers serving as current limiters 6, for protecting thebattery against overheating in the event of an internal short circuit,combined with current interrupters 8 that are thermally activatable byan increase in temperature, for irreversibly interrupting theself-discharge process in the event that the battery should overheat orachieve an or unsafe temperature.

FIGS. 2 A and 2B illustrate schematic representations of exemplaryconfigurations of film-type lithium ion batteries having one or morelayers serving as combined current limiters 6 and current interrupters8, for protecting the battery against overheating in the event of aninternal short circuit, combined with current interrupters 8 that arevoltaicly activable by an increase in voltage, for irreversiblyinterrupting the self-discharge process in the event that the batteryshould become overcharged.

FIGS. 3A and 3B illustrate schematic representations of exemplaryconfigurations of film-type lithium ion batteries having one or moreresistive layers serving a current limiters 6 for protecting the batteryagainst overheating in the event of an internal short circuit, combinedwith current interrupters 8 that are thermally activable by an increasein temperature, for irreversibly interrupting the self-discharge processin the event that the battery should overheat or achieve an or unsafetemperature, and further combined with current interrupters 8 that canbe activated by an increase in voltage, for irreversibly interruptingthe self-discharge process in the event that the battery should becomeovercharged.

FIGS. 4A-4D illustrates cross sectional views of prior art film-typelithium ion batteries (FIGS. 4A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 4C and D).

FIGS. 5A-5D illustrate cross sectional views of prior art film-typelithium ion batteries (FIGS. 5A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 5C and D).

FIGS. 6A-6D illustrate cross sectional views of prior art film-typelithium ion batteries (FIGS. 6A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 6C and D).

FIGS. 7A-7D illustrates cross sectional views of prior art film-typelithium ion batteries (FIGS. 7A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 7C and D).

FIGS. 8A-8D illustrate cross sectional views of prior art film-typelithium ion batteries (FIGS. 8A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 8C and D).

FIGS. 9A-9D illustrate cross sectional views of prior art film-typelithium ion batteries (FIGS. 9A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 9C and D).

FIGS. 10A-10D illustrate cross sectional views of prior art film-typelithium ion batteries (FIGS. 10A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 10C and D).

FIGS. 11A-11D illustrate cross sectional views of prior art film-typelithium ion batteries (FIGS. 11A and B) and of film-type lithium ionbatteries of the present disclosure (FIGS. 11C and D).

FIGS. 12A-12C illustrates exemplary structures for the combined currentlimiter 6 and current interrupter 8.

FIGS. 13A and 13B illustrate exemplified Cell compositions.

FIG. 14 illustrates the various positive electrode 14 formulations usedin chemical decomposition voltage measurements.

FIG. 15 illustrates the resistance of baseline Cell #2 at 3.6V vsgraphite in relation to the temperature increase. The resistancedecrease about 10 times with the increase in the temperature.

FIG. 16 illustrates the resistance of Cell #3 (positive electrode 14with the CaCO₃ ceramic layer) at 0, 3.646, and 4.11 respectively,voltage vs graphite in relation to the temperature increase. Theresistance increases slightly for zero voltage, and dramatically for3.646 and 4.11 V.

FIG. 17 illustrates the resistance of Cell #4 (positive electrode 14with the Al₂O₃ and CaCO₃ ceramic layer) at 0V and 3.655V, respectively,voltage vs graphite in relation to the temperature increase. Theresistance increases slightly for zero voltage, and dramatically for3.655 V.

FIG. 18 illustrates the discharge capacity of baseline Cell #1 (noresistive layer) vs the cell voltage at 1 A, 3 A, 6 A and 10 A.

FIG. 19 illustrates the discharge capacity of Cell #3 (85.2% CaCO₃ basedresistive layer 6) vs the cell voltage at 1 A, 3 A, 6 A and 10 A. Thecell discharge capability decreases significantly with the increase inthe cell discharge current with this particular resistive layer 6.

FIG. 20 summarizes the cell impedance and discharge capacities at 1 A, 3A, 6 A and 10 A and their corresponding ratios of the capacity at 3 A, 6A or 10 A over that at 1 A for Cell #1 (baseline), #3, #4, #5, and #6.The cell impedance at 1 KHz goes up with the resistive and gas-generatorlayer. The resistive layer 6 has caused the increase in the cellimpedance since all cells with the resistive layer 6 gets higherimpedance while the cell discharge capacity depends on the individualcase.

FIG. 21 illustrates the Impact Test.

FIG. 22 illustrates the cell temperature profiles during the impact testfor Cell #1 (baseline), #3, #5, and #6. The voltage of all tested cellsdropped to zero as soon as the steel rod impact the cell. All cells withthe resistive and gas-generator layer passed the test while the cellwithout any resistive layer 6 failed in the test (caught the fire). Themaximum cell temperature during the impact test is summarized in FIG.23.

FIG. 23 summarizes the cell maximum temperature in the impact test forCell #1 (baseline), #3, #4, #5, and #6.

FIG. 24 illustrates the cell voltage and temperature vs the impacttesting time for Cell #6. The impact starting time is set to 2 minutes.The cell voltage drop to zero as soon as the cell is impacted. The celltemperature is shown to increase rapidly.

FIG. 25 illustrates the cell voltage and temperature vs the overchargingtime for Cell #1 (no any protection layer). The cell voltage increasedgradually up to 40 minutes and then decreased slightly and jumped to themaximum charge voltage rapidly at about 56 minutes while at the sametime the cell temperature increased dramatically to above 600° C. Thecell voltage and temperature then dropped to a very low value due to theconnection being lost when the cell caught fire. The overcharge currentwas 2 Auntil the cell caught fire and then dropped to about 0.2 A forone or two minutes and then back to 2 A because the cell was shorted.The cell burned.

FIG. 26 illustrates the cell voltage and temperature vs the overchargingtime for the cell with Cell #3 (CaCO₃ layer). The cell voltage increasedgradually up to 40 minutes and then rapidly increased to a maximumcharge voltage of 12V at about 55 minutes. The cell temperature rapidlyincreased to above 80° C. starting at about 40 minutes and thendecreased rapidly. The over charge current decreased significantly at55° C. and kept to 0.2 A for the rest of the testing time. The cellswelled significantly after the test.

FIG. 27 illustrates the cell voltage and temperature vs the overchargingtime for Cell #5 (Na₂O₇Si₃+Al₂O₃ layer). The cell voltage increasedgradually up to 40 minutes and then rapidly increased to a maximumcharge voltage 12V at about 75 minutes. The cell overcharge voltageprofiles is very different from CaCO₃ based resistive layer 6, whichindicates the difference in the decomposition of Na₂O₇Si₃ compared withthat of CaCO₃. The cell temperature increased significantly at about 40minutes to above 75° C. and then decreased gradually. The over chargecurrent decreased significantly at 75 minutes and kept to 1 A for therest of the testing time. The cell swelled significantly after the test.

FIG. 28 summarizes the cell maximum temperature in the over charge test(2 A/12V) for Cell #1 (baseline), #3, #4, #5, and #6.

FIG. 29 illustrates the cycle life of Cell #3 (CaCO₃ resistive layer 6).The cell lost about 1.8% after 100 cycles which is lower than that ofthe cells without any resistive layer (˜2.5% by average, not shown).

FIG. 30 illustrates the cycle life of Cell #4 (CaCO₃ and Al₂O₃ resistivelayer 6). The cell lost about 1.3% after 100 cycles which is lower thanthat of the cells without any resistive layer (˜2.5% by average, notshown).

FIG. 31 illustrates the current profiles vs the voltage at roomtemperature for compounds (gas generators) containing different anionsfor potential use in rechargeable batteries with different operationvoltage. The peak current and voltages are listed in FIG. 32. The peakcurrent for Cu(NO₃)₂ was the highest while the peak current for CaCO₃was the lowest. The peak voltage for Cu(NO₃)₂ was the lowest while thepeak voltage of CaCO₃ was the highest. Therefore, Cu(NO₃)₂ may be usefulin lithium ion batteries with a relatively low operation voltage such aslithium ion cell using lithium iron phosphate positive electrode (3.7 Vas the typical maximum charging voltage). CaCO₃ may be useful in lithiumion batteries with a high operation voltage like lithium ion cell usingthe high voltage positive such as lithium cobalt oxide (4.2V as thetypical maximum charging voltage) or lithium nickel cobalt manganeseoxides (4.3 or 4.4V as the typical high charging voltage).

FIG. 32 summarizes the peak current and voltage for compounds containingdifferent anions.

FIG. 33 illustrates the current profiles vs the voltage for the polymers(organic gas generators) with or without different anions for potentialuse in rechargeable batteries with different operation voltage. PVDF isincluded as the reference. The peak current and voltages are listed inFIG. 34. The peak current for Carbopol, AI-50 and PVDF were very similarwhile CMC was the lowest. The peak voltage of Carbopol was the lowestwhile the CMC peak voltage was the highest. Therefore, Carbopolcontaining CO₃ ²⁻ anion may be useful in lithium ion batteries with arelatively low operation voltage such as lithium ion cell using lithiumiron phosphate positive electrode (3.7 V as the typical maximum chargingvoltage). CMC may be useful in lithium ion batteries with a highoperation voltage like lithium ion cell using the high voltage positivesuch as lithium cobalt oxide (4.2V as the typical maximum chargingvoltage) or lithium nickel cobalt manganese oxides (4.3 or 4.4V as thetypical high charging voltage). Water is one of CMC decompositioncompound and will react with the electrolyte and intercalated lithium inthe negative graphite electrode to generate the gases such as hydrogenfluoride (HF) and oxygen (O₂) besides being vapor or gas above 100° C.

FIG. 34 summarizes the peak current and voltage for polymers with orwithout different anions.

FIG. 35 shows cell temperature and overcharge voltage profiles during 2A/12V overcharge test at room temperature.

FIG. 36 illustrates the cell impedance and capacities at differentcurrents for Cells 1, 3, 4, 5, and 6 described in Examples 9-12 below.

FIG. 37 illustrates the resistance of Cell 2 (baseline, no resistivelayer) at 3.6V vs graphite in relation to the temperature increase. Theresistance decreased about 10 times with the increase in thetemperature.

FIG. 38 illustrates the resistance of Cell 3 at 4.09V vs graphite inrelation to the temperature increase. The resistance decreased slightlyand increased by about 3 times and then decreased by about 3 times withthe increase in the temperature.

FIG. 39 illustrates the discharge capacity of Cell 4 vs the cell voltageat 1 A, 3 A, 6 A and 10 A. The cell discharge capability decreasesdramatically with the increase in the cell discharge current with thisparticular resistive layer.

FIG. 40 illustrates the Cell temperature profiles during the impact testfor Cells 1, 3, 4, 5, and 6, as described in Examples 9-12. All cellswith the resistive layer passed the test while the cell without anyresistive layer failed in the test (caught on fire). The maximum celltemperature during the impact test is summarized in FIG. 41.

FIG. 41 illustrates the maximum temperature obtained by Cells 1, 3, 4,5, and 6 during the impact test, as described in Examples 9-12.

FIG. 42 illustrates the cycle life of Cell 3. The cell lost about 2%after 100 cycles which is similar to that of the cells without anyresistive layer (˜2.5% by average, not shown).

DETAILED DESCRIPTION

Safe, long-term operation of high energy density rechargeable batteries,including lithium ion batteries, is a goal of battery manufacturers. Oneaspect of safe battery operation is controlling the heat generated byrechargeable batteries. As described above, many factors may cause theheat generated by a rechargeable battery to exceed its heat dissipationcapacity, such as a battery defect, accident, or excessive internalcurrent. When the heat generated by a battery exceeds its ability todissipate heat, a rechargeable battery becomes susceptible to thermalrunaway, overheating, and possibly even fire or violent explosion.Described below are apparatus and methods associated with a thermallyactivated internal current interrupter that can interrupt the internalcircuit of a rechargeable battery, preventing thermal runaway.

Another aspect of safe battery operation is controlling the reactions atthe electrodes of these rechargeable batteries during both batterycharging and discharge. As described above, electrical current flowsoutside the battery, through an external circuit during use, while ionsmove from one electrode to another within the battery. In some cases,overcharge occurs and can lead to thermal runaway within the battery.Described below are apparatus and methods associated with an internalcurrent limiter that limits the rate of internal discharge in arechargeable battery when there is an internal short circuit.

A further aspect of safe battery operation is controlling the dischargeof these rechargeable batteries. As described above, a separator, orbarrier layer, is used to separate the negative and positive electrodesin rechargeable batteries in which ions can move through the battery,but electrical current is forced to flow outside the battery, through anexternal circuit. Many factors may cause the separator to be breached,and may cause a short-circuit to occur within a rechargeable battery. Ashort-circuit leads to rapid discharge and possibly overheating andthermal runaway. Described below are apparatus and methods associatedwith an internal current limiter that limits the rate of internaldischarge in a rechargeable battery when there is an internal shortcircuit.

The terminology used herein is for the purpose of describing someparticular exemplary embodiments only and is not intended to be limitingof the disclosure. As used herein, the singular forms are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising,” when used in this specification, specify thepresence of stated features, integers, steps, operations, elements,and/or components, but do not preclude the presence or addition of oneor more other features, integers, steps, operations, elements,components, and/or groups thereof.

It will be understood that, although the terms “first,” “second,” etc.may be used herein to describe various members, elements, regions,layers and/or parts, these members, elements, regions, layers and/orparts should not be limited by these terms. These terms may be usedmerely to distinguish one member, element, region, layer and/or partfrom another member, element, region, layer and/or part. Thus, forexample, a first member, element, region, layer and/or part discussedbelow could be termed a second member, element, region, layer and/orpart without departing from the teachings of the present disclosure.

FIGS. 1A-1G illustrate schematic representations of exemplaryconfigurations of film-type lithium ion batteries having one or moreresistive layers serving as current limiters (6 in FIGS. 4A-4D), forprotecting the battery against overheating in the event of an internalshort circuit, combined with current interrupters 8 that are thermallyactivatable by an increase in temperature, for irreversibly interruptingthe self-discharge process in the event that the battery should overheator achieve an or unsafe temperature. FIGS. 1A and 1C show configurationsfor batteries with a cathode current collector 101, a cathode energylayer 102, a separator 103, an anode energy layer 104, a resistivelimiter and thermal interrupt layer 105, and an anode current collector106. The configuration shown in FIG. 1B has a cathode current collector101, a cathode energy layer 102, a separator 103, a first anode energylayer 107, a resistive limiter and thermal interrupt layer 105, a secondanode energy layer 108, and an anode current collector 106. FIG. 1Dshows a configuration a cathode current collector 101, a first cathodeenergy layer 109, a separator 103, a second cathode energy layer 110, aresistive limiter and thermal interrupt layer 105, an anode energy layer104, and an anode current collector 106. FIGS. 1E-1G show configurationsfor batteries with a cathode current collector 101, a cathode energylayer 102, a separator 103, an anode energy layer 104, a first resistivelimiter and thermal interrupt layer 111, a second resistive limiter andthermal interrupt layer 112, an anode energy layer 104, and an anodecurrent collector 106.

FIGS. 2A and 2B illustrate schematic representations of exemplaryconfigurations of film-type lithium ion batteries having one or morelayers serving as combined current limiters 6 and current interrupters8, for protecting the battery against overheating in the event of aninternal short circuit, combined with current interrupters 8 that arevoltaicly activable by an increase in voltage, for irreversiblyinterrupting the self-discharge process in the event that the batteryshould become overcharged. FIG. 2A shows a configuration for a batterywith an anode current collector 201, an anode energy layer 202, aseparator 203, a cathode energy layer 204, a resistive limiter andthermal interrupt layer 205, and a cathode current collector 206. Theconfiguration shown in FIG. 2B has an anode current collector 201, ananode energy layer 202, a separator 203, a first cathode energy layer207, a resistive limiter and thermal interrupt layer 205, a secondcathode energy layer 208, and a cathode current collector 206.

FIGS. 3A and 3B illustrate schematic representations of exemplaryconfigurations of film-type lithium ion batteries having one or moreresistive layers serving a current limiters 6 for protecting the batteryagainst overheating in the event of an internal short circuit, combinedwith current interrupters 8 that are thermally activable by an increasein temperature, for irreversibly interrupting the self-discharge processin the event that the battery should overheat or achieve an or unsafetemperature, and further combined with current interrupters 8 that canbe activated by an increase in voltage, for irreversibly interruptingthe self-discharge process in the event that the battery should becomeovercharged. FIG. 3A shows a configuration for a battery with an anodecurrent collector 301, an anode energy layer 302, a separator 303, acathode energy layer 304, a resistive limiter, thermal interrupt, andvoltaic interrupt layer 305, and a cathode current collector 306. Theconfiguration shown in FIG. 3B has an anode current collector 301, ananode energy layer 302, a separator 303, a first cathode energy layer307, a resistive limiter, thermal interrupt, and voltaic interrupt layer305, a second cathode energy layer 308, and a cathode current collector306.

FIGS. 4C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A. More particularly, FIGS. 4A-4D illustrates the currentflow through film-type lithium ion batteries undergoing discharge forpowering a load (L). FIGS. 4A and C illustrate the current flow offilm-type lithium ion batteries having an intact fully operationalseparator 2 (unshorted). FIGS. 4B and D illustrate the current flow offilm-type lithium ion batteries having resistive layer serving as acurrent limiter 6, wherein the separator 2 has been short circuited by aconductive dendrite 10 penetrating therethrough. In FIGS. 4B and D, thecells are undergoing internal discharge due to a dendrite 10 penetratingthe separator 2. Note that devices with unshorted separators 2 (FIGS. 4Aand C) and the prior art device with the shorted separator 2 (FIG. 4B),current flows from one current collector 4 to the other. However, in theexemplary device of the present disclosure having a shorted separator 2and resistive layer 6 (FIG. 4D), current flow is diverted from thecurrent collector 4 and is much reduced. In FIG. 4D, the interrupter 8has not been triggered.

FIGS. 5C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A. More particularly, FIGS. 5A-5D illustrate the currentflow through film-type lithium ion batteries while it's being charged bya smart power supply (PS) that will stop the charging when it detectsthe any abnormal charge voltage. FIGS. 5A and C illustrate the currentflow of film-type lithium ion batteries having an intact fullyoperational separator 2 (unshorted). FIGS. 5B and D illustrate thecurrent flow of film-type lithium ion batteries having a separator 2shorted by a conductive dendrite 10. Note that devices with unshortedseparators 2 (FIGS. 5A and C) and the prior art device with the shortedseparator 2 (FIG. 5B), current flows from one current collector 4 to theother. However, in the exemplary device of the present disclosure havinga shorted separator 2 and resistive layer 6 (FIG. 5D), current flow isdiverted from the current collector 4 and is much reduced. In FIG. 5D,the interrupter 8 has not been triggered.

FIGS. 6C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A, after the interrupter 8 has been triggered by excessivetemperature or voltage. More particularly, FIGS. 6A-6D illustrate thecurrent flow through film-type lithium ion batteries undergoingdischarge for powering a load (L). FIGS. 6A and C illustrate the currentflow of film-type lithium ion batteries having an intact fullyoperational separator 2 (unshorted). FIGS. 6B and D illustrate thecurrent flow of film-type lithium ion batteries having a short circuitcaused by a conductive dendrite 10 penetrating the separator 2. Notethat devices with unshorted separators 2 (FIGS. 6A and C) and the priorart device with the shorted separator 2 (FIG. 6B), current flows fromone current collector 4 to the other. However, in the exemplary deviceof the present disclosure having a shorted separator 2 and both aresistive layer (current limiter 6) and a current interrupter 8 (FIG.6D), current flow is diverted from the current collector 4 and is muchreduced. In FIG. 6D, the interrupter 8 has been triggered.

FIGS. 7C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A, after the interrupter 8 has been triggered by excessivetemperature or voltage. More particularly, FIG. 7 illustrates thecurrent flow through film-type lithium ion batteries while it's beingcharged by a smart power supply (PS) which will stop the charging whenit detects any abnormal charging voltage. FIGS. 7A and C illustrate thecurrent flow of film-type lithium ion batteries having an intact fullyoperational separator 2 (unshorted). FIGS. 7B and D illustrate thecurrent flow of film-type lithium ion batteries having a having a shortcircuit caused by a separator 2 shorted by a dendrite 10. Note thatdevices with unshorted separators 2 (FIGS. 7A and C) and the prior artdevice with the shorted separator 2 (FIG. 7B), current flows from onecurrent collector 4 to the other. However, in the exemplary device ofthe present disclosure having a shorted separator 2 and resistive layer6 (current limiter 6) (FIG. 7D), current flow is diverted from thecurrent collector 4 and is much reduced. In FIG. 7D, the interrupter 8has been triggered.

FIGS. 8C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A. More particularly, FIGS. 8A-8D illustrate the currentflow through film-type lithium ion batteries undergoing discharge forpowering a load (L). FIGS. 8A and C illustrate the current flow offilm-type lithium ion batteries having an intact fully operationalseparator 2 (unshorted). FIGS. 8B and D illustrate the current flow offilm-type lithium ion batteries having resistive layer serving as acurrent limiter 6, wherein the separator 2 has been short circuited by adisruption 16. In FIGS. 8B and D, the cells are undergoing internaldischarge due to a breach 16 penetrating the separator 2. Note thatdevices with unshorted separators 2 (FIGS. 8A and C) and the prior artdevice with the shorted separator 2 (FIG. 8B), current flows from onecurrent collector 4 to the other. However, in the exemplary device ofthe present disclosure having a shorted separator 2 and resistive layer6 (FIG. 8D), current flow is diverted from the current collector 4 andis much reduced. In FIG. 8D, the interrupter 8 has not been triggered.

FIGS. 9C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A. More particularly, FIGS. 9A-9D illustrate the currentflow through film-type lithium ion batteries while it's being charged bya smart power supply (PS) that will stop the charging when it detectsany abnormal charge voltage. FIGS. 9A and C illustrate the current flowof film-type lithium ion batteries having an intact fully operationalseparator 2 (unshorted). FIGS. 9B and D illustrate the current flow offilm-type lithium ion batteries having a having a separator 2 shorted bya by a disruption 16. Note that devices with unshorted separators 2(FIGS. 9A and C) and the prior art device with the shorted separator 2(FIG. 9B), current flows from one current collector 4 to the other.However, in the exemplary device of the present disclosure having ashorted separator 2 and resistive layer 6 (FIG. 9D), current flow isdiverted from the current collector 4 and is much reduced. In FIG. 9D,the interrupter 8 has not been triggered.

FIGS. 10C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A, after the interrupter 8 has been triggered by excessivetemperature or voltage. More particularly, FIGS. 10A-10D illustrate thecurrent flow through film-type lithium ion batteries undergoingdischarge for powering a load (L). FIGS. 10A and C illustrate thecurrent flow of film-type lithium ion batteries having an intact fullyoperational separator 2 (unshorted). FIGS. 10B and D illustrate thecurrent flow of film-type lithium ion batteries having a short circuitcaused by a disruption 16. Note that devices with unshorted separators 2(FIGS. 10A and C) and the prior art device with the shorted separator 2(FIG. 10B), current flows from one current collector 4 to the other.However, in the exemplary device of the present disclosure having ashorted separator 2 and both a resistive layer (current limiter 6) and acurrent interrupter 8 (FIG. 6D), current flow is diverted from thecurrent collector 4 and is much reduced. In FIG. 10D, the interrupter 8has been triggered.

FIGS. 11C and D illustrate the film-type lithium ion batteries of FIG.1A, 2A, or 3A, after the interrupter 8 has been triggered by excessivetemperature or voltage. More particularly, FIGS. 11A-11D illustrate thecurrent flow through film-type lithium ion batteries while it's beingcharged by a smart power supply (PS) that will stop the charging when itdetects any abnormal charge voltage. FIGS. 11A and C illustrate thecurrent flow of film-type lithium ion batteries having an intact fullyoperational separator 2 (unshorted). FIGS. 11B and D illustrate thecurrent flow of film-type lithium ion batteries having a having a shortcircuit caused by a separator 2 shorted by a disruption 16. Note thatdevices with unshorted separators 2 (FIGS. 11A and C) and the prior artdevice with the shorted separator 2 (FIG. 11B), current flows from onecurrent collector 4 to the other. However, in the exemplary device ofthe present disclosure having a shorted separator 2 and resistive layer6 (current limiter 6) (FIG. 11D), current flow is diverted from thecurrent collector 4 and is much reduced. In FIG. 11D, the interrupter 8has been triggered.

FIG. 12A illustrates resistive layer 6 having a high proportion ofceramic particles coated with binder. Interstitial voids between thecoated ceramic particles render the resistive layer 6 porous. FIG. 12Billustrates resistive layer 6 having a high proportion of ceramicparticles bound together by particles of binder. Interstitial voidsbetween the coated ceramic particles render the resistive layer 6porous. FIG. 12C illustrates resistive layer 6 having an intermediateproportion of ceramic particles (less than 80%) held together withbinder. The resistive layer 6 lacks interstitial voids between thecoated ceramic particles and is non-porous.

Current Limiter

A first aspect of the disclosure is directed to an improved HEDR batteryof a type including an anode energy layer 12, a cathode energy layer 14,a separator 2 between the anode energy layer 12 and the cathode energylayer 14 for preventing internal discharge thereof, and at least onecurrent collector 4 for transferring electrons to and from either theanode or cathode energy layer. The anode and cathode energy layers eachhave an internal resistivity. The HEDR battery has a preferredtemperature range for discharging electric current and an uppertemperature safety limit. The improvement is employable, in the event ofseparator failure, for limiting the rate of internal discharge throughthe failed separator and the generation of joule heat resultingtherefrom. More particularly, the improvement comprises a resistivelayer 6 interposed between the separator and one of the currentcollectors 4 for limiting the rate of internal discharge through thefailed separator in the event of separator failure. The resistive layer6 has a fixed resistivity at temperatures between the preferredtemperature range and the upper temperature safety limit. The fixedresistivity of the resistive layer 6 is greater than the internalresistivity of either energy layer. The resistive layer 6 helps thebattery avoid temperatures in excess of the upper temperature safetylimit in the event of separator failure.

Some embodiments of the present disclosure include an improved highenergy density rechargeable battery are of a type including:

-   -   1. two electrodes (12 and 14) of opposite polarity, each        electrode characterized by its resistivity, by its safe        operating temperature range, and its safe charging voltage; the        two electrodes being subject to a risk of overcharge above the        safe charging voltage and the formation of the short circuit        therefrom; the two electrodes being subject to a risk of thermal        runaway above the safe operating temperature range.    -   2. a separator 2 for separating the two electrodes and        preventing internal discharge therebetween; the separator being        subject to a risk of forming a short circuit, the short circuit        potentially allowing a rapid internal discharge between the two        electrodes, the rapid internal discharge between the two        electrodes potentially allowing a rapid production of joule heat        therefrom, the rapid production of joule heat potentially        allowing a thermal runaway.    -   3. at least one electrode employing a current collector 4 for        transferring electrons.    -   4. a current limiter 6 forming an electrical coupling between        one of the electrodes and its corresponding current collector,        the current limiter having a resistivity for resistively        impeding current therethrough and, in the event the separator        forms the short circuit, for diverting current from the        electrode current collector to which it is coupled, and for        reducing the rate of the internal discharge between the two        electrodes.    -   5. a current interrupter 8 having an engaged configuration, an        disengaged configuration, and a gas generating component for        transitioning the current interrupter from the engaged to the        unengaged configuration, the gas generating component having a        trigger for generating a gas, the trigger being selected from        the group consisting of temperature triggers and voltage        triggers, the temperature triggers being activatable above the        safe operating temperature range; the voltage triggers being        activatable above the safe charging voltage; in the engaged        configuration, the current interrupter electrically coupling one        of the electrodes and its corresponding current collector with a        laminated connection, in the disengaged configuration, the        laminated connection becoming delaminated and the current        interrupter forming a nonconductive gap for interrupting the        electrical coupling between the electrode and its corresponding        current collector, the current interrupter transitioning from        the engaged to the disengaged configuration by triggering the        gas generating component responsive to the trigger, the        generated gas delaminating the laminated connection for        interrupting the electrical coupling between the electrode and        its corresponding current collector, whereby the current limiter        and the current interrupter, in combination, diminishing the        risk of thermal runaway resulting from separator short circuit,        electrode overcharge, and electrode overheating.

In some embodiments, the current interrupter is triggered bytemperature.

In some embodiments, the current interrupter includes a layer containinga single gas generating component triggered by temperature.

In some embodiments, the current interrupter is triggered by voltage.

In some embodiments, the current interrupter includes a layer containinga single gas generating component triggered by voltage.

In some embodiments, the current interrupter is triggered by temperatureand voltage.

In some embodiments, the current interrupter includes a layer containinga single gas generating component triggered by temperature and voltage.

In some embodiments, the current interrupter includes a layer containingtwo gas generating components, one triggered by temperature and theother triggered by voltage.

In some embodiments, the current interrupter may include a layercontaining one or more inorganic gas generating compounds that generategas at a specific temperature or voltage.

In some embodiments, the inorganic gas generating compounds are selectedfrom the group consisting of CaCO₃, La₂(CO₃)₃, Na₂SO₃, ZnCO₃Zn(OH)₂,CuCO₃Cu(OH)₂, and Cu(NO₃)₂ as disclosed in FIG. 32.

In some embodiments, the current interrupter may include a layercontaining one or more organic gas generating compounds that generategas at a specific temperature or voltage.

In some embodiments, the organic gas generating compounds are selectedfrom the group consisting of Carbopol, Torlon® AI-50, CMC, and PVDF asdisclosed in FIG. 34.

In some embodiments, the current interrupter may include a layercontaining a combination of inorganic and organic gas generatingcompounds that generate gas at a specific temperature or voltage.

In some embodiments of the improved high energy density rechargeablebattery, the current limiter and the current interrupter aresimultaneously incorporated into a protective layer interposed bylamination between the same electrode and current collector, asdisclosed in FIGS. 1A, 1C, and 2A.

In some embodiments of the improved high energy density rechargeablebattery, the current limiter and the current interrupter triggered byboth temperature and voltage are simultaneously incorporated into aprotective layer interposed by lamination between the same electrode andcurrent collector, as disclosed in FIG. 3A.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, the improvementfurther characterized wherein:

-   -   the current limiter and the current interrupter are        simultaneously incorporated into a first protective layer        interposed by lamination between the first electrode and the        first current collector; and    -   the current limiter and the current interrupter are        simultaneously incorporated into a second protective layer        interposed by lamination between the second electrode and the        second current collector,        as disclosed in FIG. 1E.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, the improvementfurther characterized wherein:

-   -   the current limiter and the current interrupter are        simultaneously incorporated into a first protective layer        interposed by lamination between the first electrode and the        first current collector; and    -   the current limiter and the current interrupter are        simultaneously incorporated into a second protective layer        interposed by lamination between the second electrode and the        separator,        as disclosed in FIG. 1F.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, the improvementfurther characterized wherein:

-   -   the current limiter and the current interrupter are        simultaneously incorporated into a first protective layer        interposed by lamination between the first electrode and the        separator; and    -   the current limiter and the current interrupter are        simultaneously incorporated into a second protective layer        interposed by lamination between the second electrode and the        second current collector,        as disclosed in FIG. 1G.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the firstelectrode including a first portion and a second portion, the secondportion of the first electrode interposed between the first portion ofthe first electrode and the first current collector, the improvementfurther characterized wherein:

-   -   1. the current limiter being layered between the first portion        of the first electrode and the second portion of the first        electrode; and    -   2. the current interrupter being layered between the second        portion of the first electrode and the first current collector.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the firstelectrode including a first portion and a second portion, the secondportion of the first electrode interposed between the first portion ofthe first electrode and the first current collector, the improvementfurther characterized, wherein the current limiter and the currentinterrupter are simultaneously incorporated into a protective layerinterposed by lamination between the first portion and the secondportion of the first electrode, as disclosed in FIGS. 1B and 2B.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the firstelectrode including a first portion and a second portion, the secondportion of the first electrode interposed between the first portion ofthe first electrode and the first current collector, the improvementfurther characterized, wherein the current limiter and the currentinterrupter triggered by both temperature and voltage are simultaneouslyincorporated into a protective layer interposed by lamination betweenthe first portion and the second portion of the first electrode, asdisclosed in FIG. 3B.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the secondelectrode including a first portion and a second portion, the firstportion of the second electrode interposed between the second portion ofthe second electrode and the second current collector, the improvementfurther characterized wherein:

-   -   1. the current limiter being layered between the first portion        of the second electrode and the second portion of the second        electrode; and    -   2. the current interrupter being layered between the second        portion of the second electrode and the second current        collector.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the secondelectrode including a first portion and a second portion, the firstportion of the second electrode interposed between the second portion ofthe second electrode and the second current collector, the improvementfurther characterized wherein:

-   -   1. the current interrupter being layered between the first        portion of the second electrode and the second portion of the        second electrode; and    -   2. the current limiter being layered between the second portion        of the second electrode and the second current collector.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the firstelectrode including a first portion and a second portion, the firstportion of the second electrode interposed between the second portion ofthe second electrode and the second current collector, the improvementfurther characterized, wherein the current limiter and the currentinterrupter are simultaneously incorporated into a protective layerinterposed by lamination between the first portion and the secondportion of the second electrode, as disclosed in FIG. 1D.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector, the two electrodesincluding a first electrode and a second electrode, and the firstelectrode including a first portion and a second portion, the secondportion of the first electrode interposed between the first portion ofthe first electrode and the first current collector, the improvementfurther characterized wherein:

-   -   1. the current limiter being layered between the second portion        of the first electrode and the first current collector; and    -   2. the current interrupter being layered between the first        portion of the first electrode and the second portion of the        first electrode.

In some embodiments, the improved high energy density rechargeablebattery is of a type having two current collectors, including a firstcurrent collector and a second current collector and the two electrodesincluding a first electrode and a second electrode, the improvementfurther characterized, wherein:

-   -   1. the current limiter being layered between the first electrode        and the first current collector; and    -   2. the current interrupter being layered between the second        electrode and the second current collector.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has a temperature range forsafe operation and an internal resistivity therein, the improvementfurther characterized wherein the current limiter having a resistivitygreater than the internal resistivity of the electrode with which thecurrent limiter is layered within the temperature range for safeoperation.

In some embodiments of the improved high energy density rechargeablebattery, the improvement further characterized, wherein the currentlimiter lacking a resistivity transition switch at temperatures withinthe temperature range for safe operation.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has a temperature range forstandard operation, the improvement further characterized, wherein thecurrent limiter having a resistivity transition with a resistivity lessthan the internal resistivity of the electrode within the temperaturerange for standard operation and a resistivity greater than the internalresistivity of the electrode above the temperature range for standardoperation.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has a temperature range forstandard operation, the improvement further characterized, wherein thecurrent interrupter is activated by temperature above the temperaturerange for standard operation.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has a temperature range forstandard operation and a temperature range for safe operation, theimprovement further characterized, wherein the current interrupter isactivated by temperature above the temperature range for standardoperation and within the temperature range for safe operation.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has an internal resistivitywithin the temperature range for safe operation, the improvement furthercharacterized, wherein the current limiter having a resistivity greaterthan the internal resistivity of the electrode with which the currentlimiter is layered within the temperature range for safe operation.

In some embodiments of the improved high energy density rechargeablebattery, the improvement further characterized, wherein the currentlimiter and the current interrupter are simultaneously incorporated intoa protective layer interposed by lamination between the same electrodeand current collector.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has a voltage range forstandard operation, the improvement further characterized, wherein thecurrent interrupter is activated by voltage above the voltage range forstandard operation.

In some embodiments, the improved high energy density rechargeablebattery is of a type, wherein each electrode has a voltage range forstandard operation and a voltage range for safe operation, theimprovement further characterized, wherein the current interrupter isactivated by voltage above the temperature range for standard operationand within the voltage range for safe operation.

In some embodiments of the improved high energy density rechargeablebattery, the improvement further characterized, wherein the currentlimiter and the current interrupter are simultaneously incorporated intoa protective layer interposed by lamination between the same electrodeand current collector.

Other embodiments of the present disclosure include an improved highenergy density rechargeable battery of a type including two electrodesof opposite polarity, a separator separating the two electrodes, and atleast one current collector electrically coupled to one of theelectrodes, the separator preventing internal discharge between the twoelectrodes, failure of the separator potentially causing an internaldischarge between the two electrodes (as illustrated in FIGS. 6A-B andFIGS. 7A-B), the internal discharge causing a generation of joule heatof potential danger, the improvement comprising:

-   -   1. a thermally activatable current interrupter and a voltage        activatable current interrupter, wherein the thermally        activatable current interrupter layered by lamination between        one of the current collectors and one of the electrodes, the        thermally activatable current interrupter, when unactivated,        electrically coupling the current collector to the electrode        with which it is layered, the current interrupter, when        activated, delaminating from the current collector for forming a        nonconductive gap for electrically decoupling the current        collector from the electrode with which it had been layered (as        illustrated in FIGS. 6C-D and FIGS. 7C-D), the electrical        decoupling slowing the rate of internal discharge between the        two electrodes in the event of separator failure;    -   2. the voltage activatable current interrupter layered by        lamination between one of the current collectors and one of the        electrodes, the voltage activatable current interrupter, when        unactivated, electrically coupling the current collector to the        electrode with which it is layered, the current interrupter,        when activated, delaminating from the current collector for        forming a nonconductive gap for electrically decoupling the        current collector from the electrode with which it had been        layered, the electrical decoupling slowing the rate of internal        discharge between the two electrodes in the event of separator        failure (as illustrated in FIGS. 6C-D and FIGS. 7C-D);        whereby, activation of either the thermally activated current        interrupter or voltage activated current interrupter in the        event of separator failure, slows the generation joule heat for        diminishing the potential danger.

Some embodiments of the present disclosure include a process foravoiding thermal runaway within a high energy density rechargeablebattery undergoing internal discharge due to separator failure, theprocess comprising delaminating an electrode within the battery from itscurrent collector by generating a gas from a heat sensitive gasgenerating material within an interrupt layer interposed between theelectrode and current collector, the delaminating electricallydecoupling the electrode from its current collector for slowing the rateof internal discharge.

Some embodiments of the present disclosure include a process foravoiding thermal runaway within a high energy density rechargeablebattery at risk of suffering from separator failure due to voltageovercharge (as illustrated in FIGS. 7A-B), the process comprisingdelaminating an electrode within the battery from its current collectorby generating a gas from a voltage sensitive gas generating materialwithin an interrupt layer interposed between the electrode and currentcollector, the delaminating electrically decoupling the electrode fromits current collector for interrupting the voltage overcharge (asillustrated in FIGS. 7C-D).

The following abbreviations have the indicated meanings:

-   -   Carbopol®-934=cross-linked polyacrylate polymer supplied by        Lubrizol Advanced Materials, Inc.    -   CMC=carboxymethyl cellulose    -   CMC-DN-800H=CMC whose sodium salt of the carboxymethyl group had        been replaced by ammonium (supplied by Daicel FineChem Ltd).    -   MCMB=mesocarbon microbeads    -   NMC=Nickel, Manganese and Cobalt    -   NMP=N-methylpyrrolidone    -   PTC=positive temperature coefficient    -   PVDF=polyvinylidene fluoride    -   SBR=styrene butadiene rubber    -   Super P®=conductive carbon blacks supplied by Timcal    -   Torlon AI-50=water soluble analog of Torlon 4000TF    -   Torlon® 4000TF=neat resin polyamide-imide (PAI) fine powder

Preparation of the resistance layer and electrode active layer isdescribed below, along with battery cell assembly.

The following is a generalized procedure for preparing a resistancelayer (first layer):

-   -   i. Dissovle the binder into an appropriate solvent.    -   ii. Add the conductive additive and ceremic powder into the        binder solution to form a slurry.    -   iii. Coat the slurry made in Step ii. onto the surface of a        metal foil, and then dry it to form a resistance layer on the        surface of the foil.

The following is a generalized procedure for the electrode preparation(on the top of the first layer):

-   -   i. Dissovle the binder into an appropriate solvent.    -   ii. Add the conductive additive into the binder solution to form        a slurry.    -   iii. Put the cathode or anode material into the slurry made in        the Step v. and mix it to form the slurry for the electrode        coating.    -   iv. Coat the electrode slurry made in the Step vi. onto the        surface of the layer from Step iii.    -   v. Compress the electrode into the design thickness.

The following is a generalized procedure for Cell assembly:

-   -   i. Dry the positive electrode at 125° C. for 10 hr and negative        electrode at 140° C. for 10 hr.    -   ii. Punch the electrodes into the pieces with the electrode tab.    -   iii. Laminate the positive and negative electrodes with the        separator as the middle layer.    -   iv. Put the flat jelly-roll made in the Step xi. into the        Aluminium composite bag.

Below are the generalized steps for conducting an impact test, as shownin FIG. 21, for a battery cell as described herein.

-   -   i. Charge the cell at 2 Aand 4.2V for 3 hr.    -   ii. Put the cell onto a hard flat surface such as concrete.    -   iii. Attach a thermal couple to the surface of the cell with        high temperature tape and connnect the positive and negative        tabs to the voltage meter.    -   iv. Place a steel rod (15.8 mm±0.1 mm in diameter×about 70 mm        long) on its side across the center of the cell.    -   v. Suspend a 9.1±0.46 Kg steel block (75 mm in diameter×290 mm        high) at a height of 610±25 mm above the cell.    -   vi. Using a containment tube (8 cm inside diameter) to guide the        steel block, release the steel block through the tube and allow        it to free fall onto the steel bar laying on the surface of the        cell causing the separator to breach while recording the        temperature.    -   vii. Leave the steel rod and steel block on the surface of the        cell until the cell temperature stablizes near room temperature.    -   viii. End test.

Below are the generalized steps for performing an overcharge test.

-   -   i. Charge the cell at 2 Aand 4.2V for 3 hr.    -   ii. Put the charged cell into a room temperature oven.    -   iii. Connect the cell to a power supply (manufactured by        Hewlett-Packard).    -   iv. Set the voltage and current on the power supply to 12V and 2        A.    -   v. Turn on the power supply to start the overcharge test while        recording the temperature and voltage.    -   vi. Test ends when the cell temperature decreases and stablizes        near room temperature.

Below are the generalized steps for performing the ResistanceMeasurement Test.

-   -   i. Place one squared copper foil (4.2×2.8 cm) with the tab on to        a metal plate (˜12×˜8 cm). Then cut a piece of thermal tape and        carefully cover the squared copper foil.    -   ii. Cut a piece of the electrode that is slightly larger than        the copper paper. Place the electrode on to the copper foil.    -   iii. Place another copper foil (4.2×2.8 cm) with tab on the        electrode surface, repeat steps i-ii with it.    -   iv. At this point, carefully put them together and cover them        using high temperature tape and get rid of any air bubble    -   v. Cut a “V” shaped piece of metal off both tabs.    -   vi. Attach the completed strip to the metal clamp and tighten        the screws. Make sure the screws are really tight.    -   vii. Attach the tabs to the connectors of Battery HiTester        (produced by Hioki USA Corp.) to measure the resistance to make        sure that a good sample has been made for the measurement.    -   viii. Put the metal clamp inside the oven, connect the “V”        shaped tabs to the connectors and then tightened the screw. Tape        the thermocouple onto the metal clamp.    -   ix. Attach the Battery HiTester to the wires from oven. Do not        mix up the positive and the negative wires.    -   x. Close the oven and set the temperature to 200° C. at 4° C.        per minute, and start the test. Record data every 15 seconds.    -   xi. Stop recording the data when the metal clamp and oven reach        just a little over 200° C.    -   xii. Turn off the oven and the Battery HiTester.    -   xiii. End Test.

Below are the generalized steps for performing the Cycle Life procedure.

-   -   i. Rest for 5 minutes.    -   ii. Discharge to 2.8V at 1 A.    -   iii. Rest for 20 minutes.    -   iv. Charge to 4.2V at 0.7 A for 270 minutes.    -   v. Rest for 10 minutes.    -   vi. Discharge to 2.8V at 0.7 A.    -   vii. Rest for 10 minutes.    -   viii. Repeat Steps iii to vii 100 times.    -   ix. End test.

Below are the generalized steps for testing a battery cell with aresistance layer for discharge at 1 A, 3 A, 6 A, and 10 A. In each test,the battery cell is tested in a chamber with controlled, constanttemperature, for example 50° C.

-   -   i. Rest for 5 minutes.    -   ii. Discharge to 2.8V at 1 A.    -   iii. Rest for 20 minutes.    -   iv. Charge to 4.2V at 0.7 A for 270 minutes.    -   v. Rest for 10 minutes.    -   vi. Discharge to 2.8V at 1 A.    -   vii. Rest for 10 minutes.    -   viii. Charge to 4.2V at 0.7 A for 270 minutes.    -   ix. Rest for 10 minutes.    -   x. Discharge to 2.8V at 3 A.    -   xi. Charge to 4.2V at 0.7 A for 270 minutes.    -   xii. Rest for 10 minutes.    -   xiii. Discharge to 2.8V at 6 A.    -   xiv. Charge to 4.2V at 0.7 A for 270 minutes.    -   xv. Rest for 10 minutes.    -   xvi. Discharge to 2.8V at 10 A.    -   xvii. Rest for 10 minutes.    -   xviii. End Test.

Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of ordinary skillin the art to which this disclosure belongs. In the event that there isa plurality of definitions for a term herein, those in this sectionprevail unless stated otherwise.

As used herein, “high energy density rechargeable (HEDR) battery” meansa battery capable of storing relatively large amounts of electricalenergy per unit weight on the order of about 50 W-hr/kg or greater andis designed for reuse, and is capable of being recharged after repeateduses. Non-limiting examples of HEDR batteries include metal-ionbatteries and metallic batteries.

As used herein, “metal-ion batteries” means any rechargeable batterytypes in which metal ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of metal-ion batteries include lithium-ion, aluminum-ion,potassium-ion, sodium-ion, magnesium-ion, and others.

As used herein, “metallic batteries” means any rechargeable batterytypes in which the anode is a metal or metal alloy. The anode can besolid or liquid. Metal ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of metallic batteries include M-S, M-NiCl₂, M-V₂O₅, M-Ag₂VP₂O₈,M-TiS₂, M-TiO₂, M-MnO₂, M-Mo₃S₄, M-MoS₆Se₂, M-MoS₂, M-MgCoSiO₄,M-Mg_(1.03)Mn_(0.97)SiO₄, and others, where M=Li, Na, K, Mg, Al, or Zn.

As used herein, “lithium-ion battery” means any rechargeable batterytypes in which lithium ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of lithium-ion batteries include lithium cobalt oxide (LiCoO₂),lithium iron phosphate (LiFePO₄), lithium cobalt phosphate (LiCoPO₄),lithium excess layered oxides such as (LiMnO₃)x(LiMO₂) (M=Ni, Co, Mn),olivines, LiMSiO₄ (M=iron, Cobalt, Nickel and Vanadium); lithiummanganese oxide (LiMn₂O₄), lithium nickel oxide (LiNiO₂), lithium nickelmanganese cobalt oxide (LiNiMnCoO₂), lithium nickel cobalt aluminumoxide (LiNiCoAlO₂), lithium titanate (Li₄Ti₅O₁₂), lithium titaniumdioxide, lithium/graphene, lithium/graphene oxide coated sulfur,lithium-sulfur, lithium-purpurin, and others. Lithium-ion batteries canalso come with a variety of anodes including silicon-carbonnanocomposite anodes and others. Lithium-ion batteries can be in variousshapes including small cylindrical (solid body without terminals), largecylindrical (solid body with large threaded terminals), prismatic(semi-hard plastic case with large threaded terminals), and pouch (soft,flat body). Lithium polymer batteries can be in a soft package or pouch.The electrolytes in these batteries can be a liquid electrolyte (such ascarbonate based or ionic), a solid electrolyte, a polymer basedelectrolyte or a mixture of these electrolytes.

As used herein, “aluminum-ion battery” means any rechargeable batterytypes in which aluminum ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of aluminum-ion batteries include Al_(n)M₂ (XO₄)₃, whereinX═Si, P, S, Mo, As, and others; and M=Fe, Ca, Mg, V, Cr and others;aluminum transition-metal oxides (Al_(x)MO₂ wherein M=Fe, Mn, Ni, Mo,Co, Cr, Ti, V and others) such as Al_(x) (V₄O₈), Al_(x)NiS₂, Al_(x)FeS₂,Al_(x)VS₂ and Al_(x)WS₂ and others.

As used herein, “potassium-ion battery” means any rechargeable batterytypes in which potassium ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of potassium-ion batteries include K_(n)M₂(XO₄)₃, wherein X═Si,P, S, Mo, As, and others; and M=Fe, Ca, Mg, V, Cr and others; potassiumtransition-metal oxides (KMO₂ wherein M=Fe, Mn, Ni, Mo, Co, Cr, Ti, Vand others), and others.

As used herein, “sodium-ion battery” means any rechargeable batterytypes in which sodium ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of sodium-ion batteries include Na_(n)M₂(XO₄)₃, wherein X═Si,P, S, Mo, As, and others; and M=Fe, Ca, Mg, V, Cr and others;NaV_(1-x)Cr_(x)PO₄F, NaVPO₄F, Na₄Fe₃(PO₄)₂(P₂O₇), Na₂FePO₄F, Na₂FeP₂O₇,Na_(2/3)[Fe_(1/2)Mn_(1/2)]O₂, Na(Ni_(1/3)Fe_(1/3)Mn_(1/3))O₂, NaTiS₂,NaFeF₃; Sodium Transition-Metal Oxides (NaMO₂ wherein M=Fe, Mn, Ni, Mo,Co, Cr, Ti, V and others) such as Na_(2/3)[Fe_(1/2)Mn_(1/2)]O₂,Na(Ni_(1/3)Fe_(1/3)Mn_(1/3))O₂, Na_(x)Mo₂O₄, NaFeO₂, Na_(0.7)CoO₂,NaCrO₂, NaMnO₂, Na_(0.44)MnO₂, Na_(0.7)MnO₂, Na_(0.7)MnO_(2.25),Na_(2/3)Mn_(2/3)Ni_(1/3)O₂, Na_(0.61)Ti_(0.48)Mn_(0.52)O₂; VanadiumOxides such as Na_(1+x)V₃O₈, Na_(x)V₂O₅, and Na_(x)VO₂ (x=0.7, 1); andothers.

As used herein, “magnesium-ion battery” means any rechargeable batterytypes in which magnesium ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of magnesium-ion batteries include Mg_(n)M₂(XO₄)₃, whereinX═Si, P, S, Mo, As, and others; and M=Fe, Ca, Mg, V, Cr and others;magnesium Transition-Metal Oxides (MgMO₂ wherein M=Fe, Mn, Ni, Mo, Co,Cr, Ti, V and others), and others.

As used herein, “silicon-ion battery” means any rechargeable batterytypes in which silicon ions move from the negative electrode to thepositive electrode during discharge and back when charging. Non-limitingexamples of silicon-ion batteries include Si_(n)M₂(XO₄)₃, wherein X═Si,P, S, Mo, As, and others; and M=Fe, Ca, Mg, V, Cr and others; SiliconTransition-Metal Oxides (SiMO₂ wherein M=Fe, Mn, Ni, Mo, Co, Cr, Ti, Vand others), and others.

As used herein, “binder” means any material that provides mechanicaladhesion and ductility with inexhaustible tolerance of large volumechange. Non-limiting examples of binders include styrene butadienerubber (SBR)-based binders, polyvinylidene fluoride (PVDF)-basedbinders, carboxymethyl cellulose (CMC)-based binders, poly(acrylic acid)(PAA)-based binders, polyvinyl acids (PVA)-based binders,poly(vinylpyrrolidone) (PVP)-based binders, and others.

As used herein, “conductive additive” means any substance that increasesthe conductivity of the material. Non-limiting examples of conductiveadditives include carbon black additives, graphite nonaqueous ultrafinecarbon (UFC) suspensions, carbon nanotube composite (CNT) additives(single and multi-wall), carbon nano-onion (CNO) additives,graphene-based additives, reduced graphene oxide (rGO), conductiveacetylene black (AB), conductive poly(3-methylthiophene) (PMT),filamentary nickel powder additives, aluminum powder, electrochemicallyactive oxides such as lithium nickel manganese cobalt oxide and others.

As used herein, “metal foil” means any metal foil that under highvoltage is stable. Non-limiting examples of metal foils include aluminumfoil, copper foil, titanium foil, steel foil, nano-carbon paper,graphene paper, carbon fiber sheet, and others.

As used herein, “ceramic powder” means any electrical insulator orelectrical conductor that hasn't been fired. Non-limiting examples ofceramic powder materials include barium titanate (BaTiO₃), zirconiumbarium titanate, strontium titanate (SrTiO₃), calcium titanate (CaTiO₃),magnesium titanate (MgTiO₃), calcium magnesium titanate, zinc titanate(ZnTiO₃), lanthanum titanate (LaTiO₃), and neodymium titanate(Nd₂Ti₂O₇), barium zirconate (BaZrO₃), calcium zirconate (CaZrO₃), leadmagnesium niobate, lead zinc niobate, lithium niobate (LiNbO₃), bariumstannate (BaSnO₃), calcium stannate (CaSnO₃), magnesium aluminumsilicate, sodium silicate (NaSiO₃), magnesium silicate (MgSiO₃), bariumtantalate (BaTa₂O₆), niobium oxide, zirconium tin titanate, silicondioxide (SiO₂), aluminum oxide (Al₂O₃), titanium dioxide (TiO₂), andothers.

As used herein, “gas generator material” means any material which willdecompose at the high temperature or high voltage to produce a gaseither directing from the gas generator material or indirectly fromreaction of the decomposition products produced from the gas generatormaterial with other materials contained within the battery (e.g. theelectrolyte and electrodes). Non-limiting examples of gas generatormaterials include inorganic carbonates such as M_(n)(CO₃)_(m),M_(n)(SO₃)_(m), M_(n)(NO₃)_(m), ¹M_(n) ²M_(n)(CO₃)_(m), NaSiO₃*H₂O,CuCO₃CU(OH)₂, and others and organic carbonates such as polymethacrylic[—CH₂—C(CH₃)(COOM)-]_(p) and polyacrylate salts [—CH₂—CH(COOM)-]_(p),and others wherein M, ¹M, ²M are independently selected from the groupconsisting of Ba, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, andZn; n is 1-3 and m is 1-4. In some embodiments, M is independentlyselected from the group consisting of an ammonium ion, pyridinium ionand a quaternary ammonium ion. In some embodiments, the gas generatormaterial may decompose to produce a liquid (e.g. water). The liquid mayreact with other materials contained within the battery to form a gasand this gas will delaminate the electrode (e.g. water reacting with theelectrolyte [LiFP₆] to form gaseous HF and lithium in the negative toform hydrogen gas (H₂)). If the temperature of the cell exceeds thevaporization temperature of the liquid, the liquid may also undergo aphase transition to form a gas and this gas will also delaminate theelectrode.

Layers were coated onto metal foils by an automatic coating machine(compact coater, model number 3R250W-2D) produced by Thank-Metal Co.,Ltd. Layers are then compressed to the desired thickness using acalender machine (model number X15-300-1-DZ) produced by BeijingSevenstar Huachuang Electronics Co., Ltd.

EXAMPLES

The disclosure will be described more in detail below using examples,but the disclosure is not limited to the examples shown below.

Example 1

Preparation of baseline electrodes, positive and negative electrodes,and the completed Cell #1 for the evaluation in the resistancemeasurement, discharge capability tests at 50° C., impact test, andcycle life test are described below.

A) Preparation of POS1A as an Example of the Positive ElectrodePreparation.

i) PVDF (21.6 g) was dissolved into NMP (250 g); ii) Carbon black (18 g)was added and mixed for 15 minutes at 6500 rpm; iii)LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂ (NMC) (560.4 g) was added to the slurryfrom Step ii and mixed for 30 minutes at 6500 rpm to form a flowableslurry; iv) Some NMP was added for the viscosity adjustment; v) Thisslurry was coated onto 15 μm aluminum foil using an automatic coatingmachine with the first heat zone set to about 80° C. and the second heatzone to about 130° C. to evaporate off the NMP. The final dried solidloading was about 15.55 mg/cm². The positive layer was then compressedto a thickness of about 117 μm. The electrode made here was consideredas zero voltage against a standard graphite electrode and was used forthe impedance measurement at 0 V in relation to the temperature, and thedry for the cell assembly.

B) Preparation of NEG2A as an Example of the Negative ElectrodePreparation

i) CMC (5.2 g) was dissolved into deionized water (˜300 g); ii) Carbonblack (8.4 g) was added and mixed for 15 minutes at 6500 rpm; iii)Negative active graphite (JFE Chemical Corporation; GraphitizedMesophase Carbon Micro Bead (MCMB) and Synthetic Graphite (TIMCAL)(378.4 g in total) were added to the slurry from Step ii and mixed for30 minutes at 6500 rpm to form a flowable slurry; iv) SBR (solid content50% suspended in water) (16.8 g) was added to the slurry formed in Stepiii and mixed at 6500 rpm for 5 min; v) The viscosity was adjusted for asmooth coating; vi) This slurry was coated onto 9 μm thick copper foilusing an automatic coating machine with the first heat zone set to about70° C. and the second heat zone to about 100° C. to evaporate off thewater. The final dried solid loading was about 9.14 mg/cm². The negativeelectrode layer was then compressed to a thickness of about 117 μm. Thenegative made was used for the dry for the cell assembly.

C) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The jelly-roll made in the Step iii was laid flat into analuminum composite bag; v) The bag from Step iv. was dried in a 70° C.vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; ix) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/20 rate for 5 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate. Undervacuum, the cell was punctured to release any gases and then resealed.The cell made here was used for grading and other tests such asdischarging capability test at 50° C., impact test, cycle life test andso on.

FIG. 15 presents the resistance in relation to the temperature increasefor the positive electrode collected from autopsying a cell with 3.6 V.The resistance decreases about ten times. FIG. 18 shows the dischargecapacity at the discharging currents 1, 3, 6, 10 A. FIG. 20 lists thecell impedance at 1 kHz and the capacity at 1 A, 3 A, 6 A and 10 Acurrents and the ratio of the capacity at 3, 6, 10 A over that at 1 A.FIG. 22 shows the cell temperature profile during the impact test. FIG.23 summarizes the cell maximum temperature in the impact test. The cellcaught the fire during the impact test. FIG. 25 shows the voltage andtemperature profiles of the cells during the 12V/2 A over charge test.The cell caught the fire during the over charge test (FIG. 28).

Example 2

Preparation of CaCO₃ based gas generator and resistive layer, positiveand negative electrodes, and the completed Cell #3 for the evaluation inthe resistance measurement, discharge capability tests at 50° C., impacttest, over charge, and cycle life test are described below.

A) Positive POS3B as an Example of a Gas Generator and Resistive Layer(1^(st) Layer) Preparation.

i) Torlon®4000TF (0.8 g) was dissolved into NMP (10 g); ii) PVDF (3.8 g)was dissolved into NMP (˜70 g); iii) The solutions prepared in Step iand ii were mixed, and then carbon black (0.32 g) was added and mixedfor 10 minutes at 6500 rpm; iv) Nano CaCO₃ powder (34.08 g) was added tothe solution from Step iii and mixed for 20 minutes at 6500 rpm to forma flowable slurry; v) This slurry was coated onto 15 μm thick aluminumfoil using an automatic coating machine with the first heat zone set toabout 135° C. and the second heat zone to about 165° C. to evaporate offthe NMP. The final dried solid loading was about 1 mg/cm².

B) Preparation of POS3A as an Example of the Positive ElectrodePreparation (2^(nd) Layer).

i) PVDF (21.6 g) was dissolved into NMP (250 g); ii) Carbon black (18 g)was added and mixed for 15 minutes at 6500 rpm; iii)LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂ (NMC) (560.4 g) was added to the slurryfrom Step ii and mixed for 30 minutes at 6500 rpm to form a flowableslurry; iv) Some NMP was added for the viscosity adjustment; v) Thisslurry was coated onto POS3B (Example 2A) using an automatic coatingmachine with the first heat zone set to about 85° C. and the second heatzone to about 135° C. to evaporate off the NMP. The final dried solidloading was about 19.4 mg/cm². The positive layer was then compressed toa thickness of about 153 μm. The electrode made here was considered aszero voltage against a standard graphite electrode and was used for theimpedance measurement at 0 V in relation to the temperature.

C) Preparation of NEG3A as an Example of the Negative ElectrodePreparation

i) CMC (13 g) was dissolved into deionized water (˜1000 g); ii) Carbonblack (20 g) was added and mixed for 15 minutes at the rate of about6500 rpm; iii) Negative active graphite (JFE Chemical Corporation;Graphitized Mesophase Carbon Micro Bead (MCMB) and Synthetic Graphite(TIMCAL) (945.92 g in total) were added to the slurry from Step ii andmixed for 30 minutes at 6500 rpm to form a flowable slurry; iv) SBR(solid content 50% suspended in water) (32 g) was added to the slurryformed in Step iii and mixed at 6500 rpm for 5 min; v) The viscosity wasadjusted for a smooth coating; vi) This slurry was coated onto 9 μmthick copper foil using an automatic coating machine with the first heatzone set to about 100° C. and the second heat zone to about 130° C. toevaporate off the water. The final dried solid loading was about 11.8mg/cm². The negative electrode layer was then compressed to a thicknessof about 159 μm. The negative made was used for the dry for the cellassembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The jelly-roll made in the Step iii was laid flat in analuminum composite bag; v) The bag from Step iv was dried in a 70° C.vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate; x)Under vacuum, the cell was punctured to release any gases and thenresealed. The cell made here was used for grading and other tests suchas discharging capability test at 50° C., impact test, cycle life testand so on.

FIG. 16 presents the resistance in relation to the temperature increasefor the positive electrode collected from autopsying cells with 0, 3.6,and 4.09 V. The resistance increases with the increase in thetemperature, especially for the positive electrodes obtained from thecell having the voltages 3.66 and 4V. FIG. 19 shows the dischargecapacity at 1, 3, and 6 A current and at 50° C. The cell capacitydecreases significantly with the increase of the current, indicating thestrong effect from the resistive layer. FIG. 20 lists the cell impedanceat 1 kHz and the capacity at 1 A, 3 A, 6 A and 10 A currents and theratio of the capacity at 3, 6, 10 A over that at 1 A. FIG. 26 presentsthe over charge profiles during the over charge test. FIG. 28 summarizethe cell maximum temperature during the over charge test and residualcurrent in the end of over charge test. FIG. 29 shows the dischargecapacity vs. the cycle number. The cell lost about 1% capacity that isabout 100% better than that (2.5%) of the baseline cell. FIG. 22 showsthe cell temperature profiles during the impact test. FIG. 23 summarizesthe cell maximum temperature in the impact test.

Example 3

Preparation of 50% Al₂O₃ and 50% CaCO₃ based gas generator and resistivelayer, positive and negative electrodes, and the completed Cell #4 forthe evaluation in the resistance measurement, discharge capability testsat 50° C., impact test, over charge and cycle life tests are describedbelow.

A) Positive POS4B as an Example of a Gas Generator and Resistive Layer(1^(st) Layer) Preparation.

i) Torlon®4000TF (0.8 g) was dissolved into NMP (10 g); ii) PVDF (3.8 g)was dissolved into NMP (˜70 g); iii) The solutions prepared in Step iand ii were mixed, and then carbon black (0.32 g) was added and mixedfor 10 minutes at 6500 rpm; iv) Nano CaCO₃ powder (17.04 g) and Al₂O₃powder (17.04 g) were added to the solution from Step iii and mixed for20 minutes at 6500 rpm to form a flowable slurry; v) This slurry wascoated onto 15 μm thick aluminum foil using an automatic coating machinewith the first heat zone set to about 135° C. and the second heat zoneto about 165° C. to evaporate off the NMP. The final dried solid loadingwas about 1 mg/cm².

B) Preparation of POS4A as an Example of the Positive ElectrodePreparation (2^(nd) Layer).

i) PVDF (21.6 g) was dissolved into NMP (250 g); ii) Carbon black (18 g)was added and mixed for 15 minutes at the rate of about 6500 rpm; iii)LiNi_(1/3)CO_(1/3)Mn_(1/3)O₂ (NMC) (560.4 g) was added to the slurryfrom Step ii and mixed for 30 minutes at 6500 rpm to form a flowableslurry; iv) Some NMP was added for the viscosity adjustment; v) Thisslurry was coated onto POS4B (Example 3A) using an automatic coatingmachine with the first heat zone set to about 85° C. and the second heatzone to about 135° C. to evaporate off the NMP. The final dried solidloading was about 19.4 mg/cm². The positive layer was then compressed toa thickness of about 153 μm. The electrode made here was considered aszero voltage against a standard graphite electrode and was used for theimpedance measurement at 0 V in relation to the temperature.

C) Preparation of NEG4A as an Example of the Negative ElectrodePreparation

i) CMC (13 g) was dissolved into deionized water (˜1000 g); ii) Carbonblack (20 g) was added and mixed for 15 minutes at 6500 rpm; iii)Negative active graphite (JFE Chemical Corporation; GraphitizedMesophase Carbon Micro Bead (MCMB) and Synthetic Graphite (TIMCAL)(945.92 g in total) were added to the slurry from Step ii and mixed for30 minutes at 6500 rpm to form a flowable slurry; iv) SBR (solid content50% suspended in water) (32 g) was added to the slurry formed in Stepiii and mixed at about 6500 rpm for 5 min; v) The viscosity was adjustedfor a smooth coating; vi) This slurry was coated onto 9 μm thick copperfoil using an automatic coating machine with the first heat zone set toabout 100° C. and the second heat zone to about 130° C. to evaporate offthe water. The final dried solid loading was about 11.8 mg/cm². Thenegative electrode layer was then compressed to a thickness of about 159μm. The negative made was used for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The jelly-roll made in the Step iii was laid flat in analuminum composite bag; v) The bag from Step iv was dried in a 70° C.vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate; x)Under vacuum, the cell was punctured to release any gases and thenresealed. The cell made here was used for grading and other tests suchas discharging capability test at 50° C., impact test, cycle life testand so on.

FIG. 20 lists the cell impedance at 1 kHz and the capacity at 1 A, 3 A,6 A and 10 A currents and the ratio of the capacity at 3 A, 6 A, and 10A over that at 1 A. FIG. 22 shows the cell temperature profiles duringthe impact test. FIG. 23 summarizes the cell maximum temperature in theimpact test. FIG. 26 shows the voltage profiles of the cell voltage andtemperature during the 12V/2 A over charge test. FIG. 28 summarizes thecell maximum cell temperatures in the over charge test.

Example 4

Preparation of Al₂O₃ and Sodium trisilicate (NaSiO₃) mixed based gasgenerator and resistive layer, positive and negative electrodes, and thecompleted Cell #5 for the evaluation in the resistance measurement,discharge capability tests at 50° C., impact test, over charge, andcycle life tests are described below.

A) Positive POS5B as an Example of a Gas Generator and Resistive Layer(1^(st) Layer) Preparation.

i) Torlon®4000TF (0.8 g) was dissolved into NMP (˜10 g); ii) PVDF (3.8g) was dissolved into NMP (60 g); iii) The solutions prepared in Step iand ii were mixed, and then carbon black (0.32 g) was added and mixedfor 10 minutes at 6500 rpm; iv) Nano Al₂O₃ powder (17.04 g) and NaSiO₃(17.04 g) were added to the solution from Step iii and mixed for 20minutes at 6500 rpm to form a flowable slurry; v) This slurry was coatedonto 15 μm thick aluminum foil using an automatic coating machine withthe first heat zone set to about 135° C. and the second heat zone toabout 165° C. to evaporate off the NMP. The final dried solid loadingwas about 0.7 mg/cm².

B) Preparation of POS5A as an Example of the Positive ElectrodePreparation (2^(nd) Layer).

i) PVDF (21.6 g) was dissolved into NMP (270 g); ii) Carbon black (18 g)was added and mixed for 15 minutes at the rate of about 6500 rpm; iii)LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂ (NMC) (560.4 g) was added to the slurryfrom Step ii and mixed for 30 minutes at the rate of about 6500 rpm toform a flowable slurry; iv) Some NMP was added for the viscosityadjustment; v) This slurry was coated onto POS5B (Example 4A) using anautomatic coating machine with the first heat zone set to about 85° C.and the second heat zone to about 135° C. to evaporate off the NMP. Thefinal dried solid loading was about 19.4 mg/cm². The positive layer wasthen compressed to a thickness of about 153 μm. The electrode made herewas considered as zero voltage against a standard graphite electrode andwas used for the impedance measurement at 0 V in relation to thetemperature.

C) Preparation of NEG5A as an Example of the Negative ElectrodePreparation

i) CMC (13 g) was dissolved into deionized water (˜1000 g); ii) Carbonblack (20 g) was added and mixed for 15 minutes at the rate of about6500 rpm; iii) Negative active graphite (JFE Chemical Corporation;Graphitized Mesophase Carbon Micro Bead (MCMB) and Synthetic Graphite(TIMCAL) (945.92 g in total) were added to the slurry from Step ii andmix for 30 minutes at 6500 rpm to form a flowable slurry; iv) SBR (solidcontent 50% suspended in water) (32 g) was added to the slurry formed inStep iii and mixed at 6500 rpm for 5 min; v) The viscosity was adjustedfor a smooth coating; vi) This slurry was coated onto 9 μm thick copperfoil using an automatic coating machine with the first heat zone set toabout 100° C. and the second heat zone to about 130° C. to evaporate offthe water. The final dried solid loading was about 11.8 mg/cm². Thenegative electrode layer was then compressed to a thickness of about 159μm. The negative made is ready for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The jelly-roll made in the Step iii was laid flat in analuminum composite bag; v) The bag from Step iv. was dried in a 70° C.vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate. x)Under vacuum, the cell was punctured to release any gases and thenresealed. The cell made here was used for grading and other tests suchas discharging capability test at 50° C., impact test, cycle life testand so on.

FIG. 18 lists the cell impedance at 1 kHz and the capacity at 1 A, 3 A,6 A and 10 A currents and the ratio of the capacity at 3, 6, and 10 Aover that at 1 A. FIG. 22 shows the cell temperature profiles during theimpact test FIG. 23 summarizes the cell maximum temperature in theimpact test. FIG. 28 summarizes the cell maximum temperature in the12V/2 A overcharge test.

Example 5

Preparation of 52% CaCO₃ and 48% PVDF based gas generator and resistivelayer, positive and negative electrodes, and the completed Cell #6 forthe evaluation in the resistance measurement, discharge capability testsat 50° C., impact test, over charge, and cycle life tests are discussedbelow.

A) Positive POS6B as an Example of a Gas Generator and Resistive Layer(1^(st) Layer) Preparation.

i) PVDF (23.25 g) was dissolved into NMP (˜250 g); ii) The solutionprepared in Step I was mixed, and then carbon black (1.85 g) was addedand mixed for 10 minutes at the rate of about 6500 rpm; iv) Nano CaCO₃powder (24.9 g) was added to the solution from Step iii and mixed for 20minutes at 6500 rpm to form a flowable slurry; v) This slurry was coatedonto 15 μm thick aluminum foil using an automatic coating machine withthe first heat zone set to about 135° C. and the second heat zone toabout 165° C. to evaporate off the NMP. The final dried solid loadingwas about 1 mg/cm².

B) Preparation of POS6A as an Example of the Positive ElectrodePreparation (2^(nd) Layer).

i) PVDF (24 g) was dissolved into NMP (300 g); ii) Carbon black (12 g)was added and mixed for 15 minutes at 6500 rpm; iii)LiNi_(0.4)Co_(0.3)Mn_(0.4)Co_(0.3)O₂ (NMC) (558 g) was added to theslurry from Step ii and mixed for 30 minutes at 6500 rpm to form aflowable slurry; iv) Some NMP was added for the viscosity adjustment; v)This slurry was coated onto POS6B (Example 5A) using an automaticcoating machine with the first heat zone set to about 85° C. and thesecond heat zone to about 135° C. to evaporate off the NMP. The finaldried solid loading was about 22 mg/cm². The positive layer was thencompressed to a thickness of about 167 μm. The electrode made here wasconsidered as zero voltage against a standard graphite electrode and wasused for the impedance measurement at 0 V in relation to thetemperature.

C) Preparation of NEG6A as an Example of the Negative ElectrodePreparation.

i) CMC (9 g) was dissolved into deionized water (˜530 g); ii) Carbonblack (12 g) was added and mixed for 15 minutes at 6500 rpm; iii)Negative active graphite (JFE Chemical Corporation; GraphitizedMesophase Carbon Micro Bead (MCMB) (564 g) were added to the slurry fromStep ii and mixed for 30 minutes at 6500 rpm to form a flowable slurry;iv) SBR (solid content 50% suspended in water) (30 g) was added to theslurry formed in Step iii and mixed at about 6500 rpm for 5 min; v) Somewater was added to adjust the viscosity for a smooth coating; vi) Thisslurry was coated onto 9 μm thick copper foil using an automatic coatingmachine with the first heat zone set to about 95° C. and the second heatzone to about 125° C. to evaporate off the water. The final dried solidloading was about 12 mg/cm². The negative electrode layer was thencompressed to a thickness of about 170 μm. The negative made was usedfor the dry for the cell assembly.

D) Preparation of Cell for the Evaluation.

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The jelly-roll made in the Step iii was laid flat in analuminum composite bag; v) The bag from Step iv was dried in a 70° C.vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate. x)Under vacuum, the cell was punctured to release any gases and thenresealed. The cell made here was used for grading and other tests suchas discharging capability test at 50° C., impact test, cycle life testand so on.

FIG. 20 lists the cell impedance at lkHz and the capacity at 1 A, 3 A, 6A and 10 A currents and the ratio of the capacity at 3, 6, 10 A overthat at 1 A. FIG. 22 shows the cell temperature profiles during theimpact test. FIG. 23 summarizes the cell maximum temperature in theimpact test. FIG. 28 summarizes the cell maximum cell temperatures inthe over charge test.

Example 6

Preparation of positive electrodes for chemical decomposition voltagemeasurements is described below.

POS7B was prepared as follows: (i) Deionized water (˜300 g) was mixedinto Carbopol®-934 (19.64 g); (ii) Super-P® (160 mg) and LiOH (200 mg)were added into the slurry made in Step (i) and mixed for 30 minutes at5000 rpm; (iii) An appropriate amount of deionized water was added toadjust the slurry to form a coatable slurry. (iv) The slurry was coatedonto a 15 μm aluminum foil with the automatic coating machine with thedrying temperatures set to 135° C. for zone 1 and 165° C. for zone 2.The final dried solid loading was about 0.7 mg/cm².

POS8B was prepared as follows: (i) Deionized water (−100 g) was mixedinto AI-50 (19.85 g); (ii) Super-P® (160 mg) was added into the slurrymade in Step (i) and mixed for 30 minutes at 5000 rpm; (iii) Anappropriate amount of deionized water was added to adjust the slurry toform a coatable slurry. (iv) The slurry was coated onto 15 μm aluminumfoil with automatic coating machine with the drying temperatures set to135 for zone 1 and 165° C. for zone 2. The final dried solid loading wasabout 0.7 mg/cm².

POS9B was prepared as follows: (i) Deionized water (˜322 g) was mixedinto 19.85 g CMC-DN-800H; (ii) Super-P® (160 mg) was added into theslurry made in Step (i) and mixed for 30 minutes at 5000 rpm; (iii) Anappropriate amount of deionized water was added to adjust the slurry toform a coatable slurry. (iv) The slurry was coated onto 15 μm aluminumfoil with automatic coating machine with the drying temperatures set to135 for zone 1 and 165° C. for zone 2. The final dried solid loading wasabout 0.7 mg/cm².

POS13B was prepared as follows: (i) Torlon® 4000TF (300 mg) wasdissolved into NMP (3 g). (ii) PVDF-A (2.4 g) was dissolved into NMP (30g). (iii) The two solutions were mixed and Super-P® (160 mg) was added,then mixed for 30 minutes at 5000 rpm. (iv) La₂(CO₃)₃ (17.04 g) or thesalts listed in FIG. 8 were added into above slurry and mixed togetherat 5000 rpm for 30 min. (v) The slurry was coated onto 15 μm aluminumfoil with automatic coating machine at first heat zone set to 13° C. andsecond heat zone to 16° C. for evaporate off the NMP. Final dried solidloading was about 0.7 mg/cm².

Example 7

Electrochemical test for the positives electrodes coated with gasgenerator layers is described below.

The decomposition voltages of all resistive layers were measured with athree electrode configuration (resistive layer as the working electrode,and lithium metal as both reference electrode and count electrode) byLinear Sweep Voltammetry technology using a VMP2 multichannelpotentiostat instrument at room temperature. A 0.3 cm×2.0 cm piece ofthe resistive layer was the working electrode, and 0.3 cm×2.0 cm pieceof lithium metal was both reference electrode and counter electrode.These electrodes were put into a glass containing LiPF₆ ethylenecarbonate based electrolyte (5 g). The scan rate is 5 mV/second in thevoltage range from 0 to 6V. FIGS. 31 and 33 shows the decompositionvoltage profiles of these compounds. FIGS. 32 and 34 summarizes the peakcurrent and peak voltage for each of the compounds tested.

Example 8

Preparation of CaCO₃ based gas generator layer, positive and negtaiveelectrodes, and the cell (#7) for the evaluation in the over charge testis described below. This gas generator layer could become a resitivelayer if the conductive additive content is in the certain range suchthat the resistivity of the gas-generater layer is more resistive (50%more at least) than that of the energy layer or the layer that providethe majority (>50%) of the battery discharge energy. The gas generatorcontent can be 2% to 99%.

A) Positive POS071A as an Example of a Gas Generator Layer (1^(st)Layer) Preparation.

i) Torlon®4000TF (0.9 g) was dissolved into NMP (10 g); ii) PVDF (5.25g) was dissolved into NMP (˜68 g); iii) The solutions prepared in Step iand ii were mixed, and then carbon black (1.8 g) was added and mixed for10 min at the rate of about 6500 rpm; iv) Nano CaCO₃ powder (7.11 g) and134.94 g LiNi_(0.33)Al_(0.33)Co_(0.33)O₂ were added to the solution fromStep iii and mixed for 20 min at the rate of about 6500 rpm to form aflowable slurry; v) This slurry was coated onto 15 μm thick aluminumfoil using an automatic coating machine with the first heat zone set toabout 90° C. and the second heat zone to about 140° C. to evaporate offthe NMP. The final dried solid loading was about 4 mg/cm².

B) Preparation of POS071B as an Example of the Positive ElectrodePreparation (2nd Layer).

i) PVDF (25.2 g) was dissolved into NMP (327 g); ii) Carbon black (21 g)was added and mixed for 15 min at the rate of about 6500 rpm; iii)LiNi_(0.82)Al_(0.03)Co_(0.15)O₂ (NCA) (649 g) was added to the slurryfrom Step ii and mixed for 30 min at the rate of about 6500 rpm to forma flowable slurry; iv) Some NMP was added for the viscosity adjustment;v) This slurry was coated onto POS071A using an automatic coatingmachine with the first heat zone set to about 85° C. and the second heatzone to about 135° C. to evaporate off the NMP. The final dried solidloading is about 20.4 mg/cm². The positive layer was then compressed toa thickness of about 155 μm.

C) Preparation of NEG015B as an Example of the Negative ElectrodePreparation

i) CMC (15 g) was dissolved into deionized water (˜951 g); ii) Carbonblack (15 g) was added and mixed for 15 min at the rate of about 6500rpm; iii) Negative active graphite (JFE Chemical Corporation;Graphitized Mesophase Carbon Micro Bead (MCMB) (945 g) was added to theslurry from Step ii and mixed for 30 min at the rate of about 6500 rpmto form a flowable slurry; iv) SBR (solid content 50% suspended inwater) (50 g) was added to the slurry formed in Step iii and mixed atabout 6500 rpm for 5 min; v) The viscosity was adjusted for a smoothcoating; vi) This slurry was coated onto 9 μm thick copper foil using anautomatic coating machine with the first heat zone set to about 100° C.and the second heat zone to about 130° C. to evaporate off the water.The final dried solid loading was about 11 mg/cm². The negativeelectrode layer was then compressed to a thickness of about 155 μm. Thenegative made is ready for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at ˜125° C. for 10 hr and negativeelectrode at ˜140° C. for 10 hr; iii) The positive and negativeelectrodes were laminated with the separator as the middle layer; iv)The jelly-roll made in the Step iii was laid flat in an aluminumcomposite bag; v) The bag from Step iv. was dried in a 70° C. vaccumoven; vi) The bag from Step v was filled with the carbonate basedelectrolyte; vii) The bag from Step vi was sealed; viii) Rest for 16hours; ix) The cell was charged to 4.2V at C/50 rate for 8 hours andthen to 4.2V at 0.5 C rate for 2 hours, then rest for 20 minutes, thendischarged to 2.8V at 0.5 C rate. The cell made here was used forgrading and other tests such as over chrage test.

FIG. 35 presents the overcharge voltage, cell temperature and ovenchamber temperature during the overcharge test (2 A and 12V). The cellpassed the over test nicely since the cell maximum temperature is about83° C. during the overcharge test. Implementations of the currentsubject matter can include, but are not limited to, articles ofmanufacture (e.g. apparatuses, systems, etc.), methods of making or use,compositions of matter, or the like consistent with the descriptionsprovided herein.

Example 9

Preparation of Al₂O₃ based resistive layer, positive and negativeelectrodes, and the completed Cell 3 for the evaluation in theresistance measurement, discharge capability tests at 50° C., impacttest, and cycle life test are described below.

A) Positive POS3B as an Example of a Resistance Layer (1^(st) Layer)Preparation.

i) Dissolve Torlon® 4000TF (1 g) into NMP (10 g); Dissolve PVDF (6 g)into NMP (70 g); iii) Mix solution prepared in Step i and ii, and thenadd carbon black (0.4 g) and mix for 10 min at 6500 rpm; iv) Add nanoAl₂O₃ powder (32 g) to the solution from Step iii and mix for 20 min atthe rate of 6500 rpm to form a flowable slurry; v) Coat this slurry onto15 μm thick aluminum foil using an automatic coating machine with thefirst heat zone set to about 130° C. and the second heat zone to about160° C. to evaporate off the NMP. The final dried solid loading is about1 mg/cm².

B) Preparation of POS3A as an Example of the Positive ElectrodePreparation (2nd Layer).

i) PVDF (21.6 g) was dissolved into NMP (250 g); Carbon black (18 g) wasadded and mixed for 15 min at 6500 rpm; LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂(NMC) (560.4 g) was added to the slurry from Step ii and mixed for 30min at 6500 rpm to form a flowable slurry; iv) Some NMP was added forthe viscosity adjustment; v) This slurry was coated onto POS3B using anautomatic coating machine with the first heat zone set to about 85° C.and the second heat zone to about 135° C. to evaporate off the NMP. Thefinal dried solid loading was about 19.4 mg/cm². The positive layer wasthen compressed to a thickness of about 153 μm. The electrode made hereis called as zero voltage against a standard graphite electrode and wasused for the impedance measurement at 0 V in relation to thetemperature.

C) Preparation of NEG3A as an Example of the Negative ElectrodePreparation

i) CMC (13 g) was dissolved into deionized water (˜1000 g); ii) Carbonblack (20 g) was added and mixed for 15 min at 6500 rpm; iii) Negativeactive graphite (JFE Chemical Corporation; Graphitized Mesophase CarbonMicro Bead (MCMB) and Synthetic Graphite (TIMCAL) (945.92 g in total)was added to the slurry from Step ii and mixed for 30 min at 6500 rpm toform a flowable slurry; iv) SBR (solid content 50% suspended in water)(32 g) was added to the slurry formed in Step iii and mixed at 6500 rpmfor 5 min; v) The viscosity was adjusted for a smooth coating; vi) Thisslurry was coated onto 9 gm thick copper foil using an automatic coatingmachine with the first heat zone set to about 100° C. and the secondheat zone to about 130° C. to evaporate off the water. The final driedsolid loading was about 11.8 mg/cm². The negative electrode layer wasthen compressed to a thickness of about 159 μm. The negative made wasused for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with the electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The flat jelly-roll made in the Step iii. was laid flat intoan aluminum composite bag; v) The bag from Step iv. was dried in a 70°C. vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rested for 16 hours; ix) The cell was charged to4.2V at C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2hours, then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate.Under vacuum, the cell was punctured to release any gases and thenresealed. The cell made here was used for grading and other tests suchas discharging capability test at 50° C., impact test, cycle life testand so on.

FIG. 38 presents the resistance in relation to the temperature increasefor the positive electrode collected from autopsying a cell with 4.09V.The resistance changes very little compared with that (FIG. 37) of thebaseline cell. FIG. 42 shows the discharge capacity vs. the cyclenumber. The cell lost about 2% capacity that is similar to that (2.5%)of the baseline cell. FIG. 36 lists the cell impedance at 1 kHz and thecapacity at 1 A, 3 A, 6 A and 10 A currents and the ratio of thecapacity at 3 A, 6 A, 10 A over that at 1 A. FIG. 40 shows the celltemperature profiles during the impact test. FIG. 41 summarizes the cellmaximum temperature in the impact test.

Example 10

Preparation of 50% Polyacrylic latex and 50% Barium Tatanate (BaTiO2)based resistive layer, positive and negative electrodes, and thecompleted Cell 4 for the evaluation in the resistance measurement,discharge capability tests at 50° C., impact test, and cycle life testare described below.

A) Positive POS4B as an Example of a Resistance Layer (1^(st) Layer)Preparation.

i) CMC (0.375 g) was dissolved into deionized water (˜30 g); ii) Thesolution prepared in Step i was mixed, and then carbon black (1.75 g)was added and mixed for several minutes; iii) nano BaTiO₂ powder (25 g)was added to the solution from Step ii and mixed for 20 min at 6500 rpmto form a flowable slurry; v) This slurry was coated onto 15 μm thickaluminum foil using an automatic coating machine with the first heatzone set to about 90° C. and the second heat zone to about 140° C. toevaporate off the water. The final dried solid loading was about 0.7mg/cm².

B) Preparation of POS4A as an Example of the Positive ElectrodePreparation (2^(nd) Layer).

i) PVDF (14.4 g) was dissolved into NMP (˜160 g); ii) Carbon black (12g) was added and mixed for 15 min at 6500 rpm; iii)LiNi_(0.5)Mn_(0.3)O_(0.2)O₂ (NMC) (373.6 g) was added to the slurry fromStep ii and mixed for 30 min at 6500 rpm to form a flowable slurry; iv)Some NMP was added for the viscosity adjustment; v) This slurry wascoated onto POS4B (Example 2A) using an automatic coating machine withthe first heat zone set to about 80° C. and the second heat zone toabout 130° C. to evaporate off the NMP. The final dried solid loadingwas about 15.2 mg/cm². The positive layer was then compressed to athickness of about 113 μm. The electrode made here was called as zerovoltage against a standard graphite electrode and was used for theimpedance measurement at 0 V in relation to the temperature.

C) Preparation of NEG3A as an Example of the Negative ElectrodePreparation

i) CMC (7.8 g) was dissolved into deionized water (˜800 g); ii) Carbonblack (12 g) was added and mixed for 15 min at 6500 rpm; iii) Negativeactive graphite (JFE Chemical Corporation; Graphitized Mesophase CarbonMicro Bead (MCMB) and Synthetic Graphite (TIMCAL) (568.6 g in total) wasadded to the slurry from Step ii and mixed for 30 min at 6500 rpm toform a flowable slurry; iv) SBR (solid content 50% suspended in water)(25.2 g) was added to the slurry formed in Step iii and mixed at 6500rpm for 5 min; v) The viscosity was adjusted for a smooth coating; vi)This slurry was coated onto 9 μm thick copper foil using an automaticcoating machine with the first heat zone set to about 70° C. and thesecond heat zone to about 100° C. to evaporate off the water. The finaldried solid loading was about 8.99 mg/cm². The negative electrode layerwas then compressed to a thickness of about 123 μm. The negative madewas used for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The flat jelly-roll made in the Step iii. was laid flat intothe aluminum composite bag; v) The bag from Step iv. was dried in a 70°C. vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate. Undervacuum, the cell was punctured to release any gases and then resealed.The cell made here was used for grading and other tests such asdischarging capability test at 50° C., impact test, cycle life test andso on.

FIG. 39 shows the discharge capacity at 1 A, 3A, 6 A current and at 50°C. The cell capacity decreases very rapidly with the increase of thecurrent, indicating the strong effect from the resistive layer. FIG. 36lists the cell impedance at 1 kHz and the capacity at 1 A, 3 A, 6 A and10 A currents and the ratio of the capacity at 3 A, 6 A, 10 A over thatat 1 A. FIG. 40 shows the cell temperature profiles during the impacttest. FIG. 41 summarizes the cell maximum temperature in the impacttest.

Example 11

Preparation of resistive layer in negative electrodes, positive andnegative electrodes, and the completed Cell 5 for the evaluation in theresistance measurement, discharge capability tests at 50° C., impacttest, and cycle life test are described below.

A) Preparation of POS5A as an Example of the Positive ElectrodePreparation.

i) PVDF (31.5 g) was dissolved into NMP (˜340 g); ii) Carbon black (13.5g) was added and mixed for 15 min at 6500 rpm; iii)LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂ (NMC) (855 g) was added to the slurryfrom Step ii and mix for 30 min at 6500 rpm to form a flowable slurry;iv) Some NMP was added for the viscosity adjustment; v) This slurry wasadded onto 15 μm aluminum foil using an automatic coating machine withthe first heat zone set to about 80° C. and the second heat zone toabout 130° C. to evaporate off the NMP. The final dried solid loadingwas about 14.8 mg/cm². The positive layer was then compressed to athickness of about 113 μm. The electrode made here was designated aszero voltage against a standard graphite electrode and was used for theimpedance measurement at 0 V in relation to the temperature, and the dryfor the cell assembly.

B) Preparation of NEG5B as an Example of the Negative ElectrodePreparation (1^(st) Layer)

CMC (0.375 g) was dissolved into deionized water (˜90 g); ii) Carbonblack (1.75 g) was added and mixed for 15 min; BaTiO₂ (25 g in total)was added to the slurry from Step ii and mixed for 30 min at 6500 rpm toform a flowable slurry; iv) SBR (solid content 50% suspended in water)(35.6 g) was added to the slurry formed in Step iii and mixed at about6500 rpm for 5 min; v) The viscosity was adjusted for a smooth coating;vi) This slurry was coated onto 9 μm thick copper foil using anautomatic coating machine with the first heat zone set to about 90° C.and the second heat zone to about 140° C. to evaporate off the water.

C) Preparation of NEG5A as an Example of the Negative ElectrodePreparation (2^(nd) Layer)

i) CMC (3.9 g) was dissolved into deionized water (˜350 g); ii) Carbonblack (6 g) was added and mixed for 15 min at 6500 rpm; iii) Negativeactive graphite (JFE Chemical Corporation; Graphitized Mesophase CarbonMicro Bead (MCMB) and Synthetic Graphite (TIMCAL) (283.8 g in total)were added to the slurry from Step ii and mixed for 30 min at 6500 rpmto form a flowable slurry; iv) SBR (solid content 50% suspended inwater) (25.2 g) was added to the slurry formed in Step iii and mixed at6500 rpm for 5 min; v) The viscosity was adjusted for a smooth coating;vi) This slurry was coated onto NEG5B (Example 4B) using an automaticcoating machine with the first heat zone set to about 70° C. and thesecond heat zone to about 100° C. to evaporate off the water. The finaldried solid loading was about 9.8 mg/cm². The negative electrode layerwas then compressed to a thickness of about 114 μm. The negative madewas used for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with the electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The flat jelly-roll made in the Step iii. was laid flat intothe aluminum composite bag; v) The bag from Step iv. was dried in a 70°C. vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/20 rate for 5 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate. Undervacuum, the cell was punctured to release any gases and then resealed.The cell made here was used for grading and other tests such asdischarging capability test at 50° C., impact test, cycle life test andso on.

FIG. 36 lists the cell impedance at 1 kHz and the capacity at 1 A, 3 A,6 A and 10 A currents and the ratio of the capacity at 3 A, 6 A, 10 Aover that at 1 A. FIG. 40 shows the cell temperature profile during theimpact test. FIG. 41 summarizes the cell maximum temperature in theimpact test.

Example 12

Preparation of Al₂O₃ and Sodium trisilicate (NaSiO₃) mixed basedresistive layer, positive and negative electrodes, and the completedCell 6 for the evaluation in the resistance measurement, dischargecapability tests at 50° C., impact test, and cycle life test aredescribed below.

A) Positive POS6B as an example of a resistance layer (1^(st) layer)preparation.

i) Torlon® 4000TF (0.8 g) was dissolved into NMP (˜10 g); ii) PVDF (3.8g) was dissolved into NMP (60 g); iii) The solutions prepared in Step iand ii were mixed, and then carbon black (0.32 g) was added and mixedfor 10 min at 6500 rpm; iv) nano Al₂O₃ powder (17.04 g) and NaSiO₃(17.04 g) were added to the solution from Step iii and mixed for 20 minat 6500 rpm to form a flowable slurry; v) This slurry was coated onto 15μm thick aluminum foil using an automatic coating machine with the firstheat zone set to about 135° C. and the second heat zone to about 165° C.to evaporate off the NMP. The final dried solid loading was about 0.7mg/cm².

B) Preparation of POS6A as an Example of the Positive ElectrodePreparation (2^(nd) Layer).

i) PVDF (21.6 g) was dissolved into NMP (270 g); ii) Carbon black (18 g)was added and mixed for 15 min at 6500 rpm; iii)LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂ (NMC) (560.4 g) was added to the slurryfrom Step ii and mixed for 30 min at 6500 rpm to form a flowable slurry;iv) Some NMP was added for the viscosity adjustment; v) This slurry wascoated onto POS6B (Example 1A) using an automatic coating machine withthe first heat zone set to about 85° C. and the second heat zone toabout 135° C. to evaporate off the NMP. The final dried solid loadingwas about 19.4 mg/cm². The positive layer was then compressed to athickness of about 153 μm. The electrode made here was called as zerovoltage against a standard graphite electrode and was used for theimpedance measurement at 0 V in relation to the temperature.

C) Preparation of NEG6A as an Example of the Negative ElectrodePreparation

i) CMC (13 g) was dissolved into deionized water (˜1000 g); ii) Carbonblack (20 g) was added and mixed for 15 min at 6500 rpm; iii) Negativeactive graphite (JFE Chemical Corporation; Graphitized Mesophase CarbonMicro Bead (MCMB) and Synthetic Graphite (TIMCAL) (945.92 g in total)were added to the slurry from Step ii and mix for 30 min at 6500 rpm toform a flowable slurry; iv) SBR (solid content 50% suspended in water)(42 g) was added to the slurry formed in Step iii and mixed at 6500 rpmfor 5 min; v) The viscosity was adjusted for a smooth coating; vi) Thisslurry was coated onto 9 μm thick copper foil using an automatic coatingmachine with the first heat zone set to about 100° C. and the secondheat zone to about 130° C. to evaporate off the water. The final driedsolid loading was about 11.8 mg/cm². The negative electrode layer wasthen compressed to a thickness of about 159 μm. The negative made isready for the dry for the cell assembly.

D) Preparation of Cell for the Evaluation

i) The electrodes were punched into the pieces with an electrode tab;ii) The positive electrode was dried at 125° C. for 10 hours andnegative electrode at 140° C. for 10 hours; iii) The positive andnegative electrodes were laminated with the separator as the middlelayer; iv) The flat jelly-roll made in the Step iii. was put into analuminum composite bag; v) The bag from Step iv. was dried in a 70° C.vacuum oven; vi) The bag from Step v was filled with the LiPF₆containing organic carbonate based electrolyte; vii) The bag from Stepvi was sealed; viii) Rest for 16 hours; ix) The cell was charged to 4.2Vat C/50 rate for 8 hours and then to 4.2V at 0.5 C rate for 2 hours,then rest for 20 minutes, then discharged to 2.8V at 0.5 C rate. Undervacuum, the cell was punctured to release any gases and then resealed.The cell made here was used for grading and other tests such asdischarging capability test at 50° C., impact test, cycle life test andso on.

FIG. 36 lists the cell impedance at 1 kHz and the capacity at 1 A, 3 A,6 A and 10 A currents and the ratio of the capacity at 3 A, 6 A, 10 Aover that at 1 A. FIG. 40 shows the cell temperature profiles during theimpact test. FIG. 41 summarizes the cell maximum temperature in theimpact test.

In the descriptions above and in the claims, phrases such as “at leastone of” or “one or more of” may occur followed by a conjunctive list ofelements or features. The term “and/or” may also occur in a list of twoor more elements or features. Unless otherwise implicitly or explicitlycontradicted by the context in which it used, such a phrase is intendedto mean any of the listed elements or features individually or any ofthe recited elements or features in combination with any of the otherrecited elements or features. For example, the phrases “at least one ofA and B;” “one or more of A and B;” and “A and/or B” are each intendedto mean “A alone, B alone, or A and B together.” A similarinterpretation is also intended for lists including three or more items.For example, the phrases “at least one of A, B, and C;” “one or more ofA, B, and C;” and “A, B, and/or C” are each intended to mean “A alone, Balone, C alone, A and B together, A and C together, B and C together, orA and B and C together.” Use of the term “based on,” above and in theclaims is intended to mean, “based at least in part on,” such that anunrecited feature or element is also permissible.

The subject matter described herein can be embodied in systems,apparatus, methods, and/or articles depending on the desiredconfiguration. The implementations set forth in the foregoingdescription do not represent all implementations consistent with thesubject matter described herein. Instead, they are merely some examplesconsistent with aspects related to the described subject matter.Although a few variations have been described in detail above, othermodifications or additions are possible. In particular, further featuresand/or variations can be provided in addition to those set forth herein.For example, the implementations described above can be directed tovarious combinations and subcombinations of the disclosed featuresand/or combinations and subcombinations of several further featuresdisclosed above. In addition, the logic flows depicted in theaccompanying figures and/or described herein do not necessarily requirethe particular order shown, or sequential order, to achieve desirableresults. Other implementations may be within the scope of the followingclaims.

What is claimed is:
 1. A battery, comprising: a current collector; andan electrode electrically coupled with the current collector via alaminated connection, wherein the electrode includes a heat-sensitivematerial configured to respond to an activation of at least atemperature trigger by at least generating a liquid that vaporizes toform a gas, wherein the gas interrupts the laminated connection betweenthe current collector and the electrode by at least causing theelectrode to delaminate from the current collector, wherein theelectrode delaminating from the current collector forms a nonconductivegap between the electrode and the current collector by at leastseparating the electrode from the current collector, wherein theformation of the nonconductive gap causes an electrical decoupling ofthe electrode and the current collector, and wherein the electricaldecoupling of the electrode and the current collector interrupts acurrent flow within the battery.
 2. The battery of claim 1, wherein thegas comprises a fire retardant gas.
 3. The battery of claim 1, whereinthe gas is further formed by a reaction between the liquid and thecurrent collector, a separator, and/or an electrolyte comprising thebattery.
 4. The battery of claim 1, further comprising a currentlimiter.
 5. The battery of claim 4, wherein the current limiter isinterposed between the electrode and the current collector.
 6. Thebattery of claim 4, wherein a resistivity of the current limiter isgreater than an internal resistivity of the electrode at temperaturesabove a temperature range for standard operation, and wherein theresistivity of the current limiter is less than the internal resistivityof the electrode at temperatures within the temperature range forstandard operation.
 7. The battery of claim 6, wherein the resistivityof the current limiter does not transition at temperatures within thetemperature range for standard operation.
 8. The battery of claim 1,wherein the electrode is further configured to delaminate from thecurrent collector in response to an activation of a voltage trigger. 9.The battery of claim 1, wherein the electrode is further configured todecompose upon the activation of at least the temperature trigger, andwherein the decomposition of the electrode further interrupts thecurrent flow within the battery.
 10. The battery of claim 1, wherein thetemperature trigger is activated when temperature exceeds a temperaturerange for standard operation.
 11. The battery of claim 1, wherein theelectrode comprises an anode or a cathode of the battery.
 12. Thebattery of claim 1, wherein the electrode further comprises anelectrochemically active material.
 13. The battery of claim 12, whereinthe electrochemically active material comprises lithium (Li), aluminum(Al), potassium (K), sodium (Na), magnesium (Mg), and/or silicon (Si).14. The battery of claim 1, wherein the heat sensitive materialcomprises an organic carbonate and/or an inorganic carbonate.
 15. Thebattery of claim 1, wherein the heat sensitive material comprises abarium (Ba) carbonate, a calcium (Ca) carbonate, a cadmium (Cd)carbonate, a cobalt (Co) carbonate, a copper (Cu) carbonate, an iron(Fe) carbonate, a potassium (K) carbonate, a lithium (Li) carbonate, amagnesium (Mg) carbonate, a manganese (Mn) carbonate, a sodium (Na)carbonate, a nickel (Ni) carbonate, a lead (Pb) carbonate, a strontium(Sr) carbonate, and/or a zinc (Zn) carbonate.
 16. A method, comprising:forming a nonconductive gap between an electrode and a current collectorwithin a battery, wherein the electrode and the current collector areelectrically coupled via a laminated connection, wherein the electrodeincludes a heat-sensitive material configured to respond to anactivation of at least a temperature trigger by at least generating aliquid that vaporizes to form a gas, wherein the gas interrupts thelaminated connection between the current collector and the electrode byat least causing the electrode to delaminate from the current collector,wherein the electrode delaminating from the current collector forms thenonconductive gap between the electrode and the current collector by atleast separating the electrode from the current collector, wherein theformation of the nonconductive gap electrically decouples the electrodeand the current collector, and wherein the electrical decoupling of theelectrode and the current collector interrupts a current flow within thebattery.